Transition metal complex

ABSTRACT

Disclosed is transition metal complex that serves as a catalytic component with which 1-hexene can be produced efficiently with excellent selectivity, even under high temperature conditions, by means of an ethylene trimerization reaction. Said transition metal complex is represented by the following general formula (1), wherein M 1  represents a Group 4 transition metal atom, and R 1  through R 11  and X 1  through X 3  each independently represent a hydrogen atom, a halogen atom, or a specific organic group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Division of co-pending U.S. patent applicationSer. No. 13/498,980, filed Mar. 29, 2012, which is a Section 371International Application No. PCT/JP2010/067127, filed Sep. 30, 2010,which was published in the Japanese language on Apr. 7, 2011, underInternational Publication No. WO 2011/040555 A1, the disclosures ofwhich are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a transition metal complex, a processfor producing the transition metal complex, a trimerization catalyst, aprocess for producing 1-hexene, a process for producing an ethylenicpolymer, a substituted cyclopentadiene compound and a process forproducing the substituted cyclopentadiene compound.

BACKGROUND ART

An α-olefin is an industrially important raw material monomer that isproduced by the oligomerization of ethylene using a metal catalyst.However, the oligomerization of ethylene usually gives α-olefin mixturesaccording to Shultz-Flory distribution. Therefore, the development of acatalyst system capable of selectively producing α-olefin is veryimportant industrially.

For example, PATENT DOCUMENT 1 has reported that a half-metallocenetitanium complex represented by the formula (Cp-B(R)_(n)Ar)TiR¹ ₃ worksas a catalytic component for selective trimerization of ethylene in thepresence of an activating co-catalytic component.

Among these catalysts for selective ethylene trimerization, ahalf-metallocene titanium complex comprising cyclopentadiene bonded to asubstituted aryl group via a carbon atom, such as[1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titaniumtrichloride, has been reported to work as an efficient ethylenetrimerization catalyst under condition of 30° C. with MAO(methylaluminoxane) as an activating co-catalytic component (see e.g.,NON-PATENT DOCUMENT 1). On the other hand,[dimethylphenylsilylcyclopentadienyl]titanium trichloride comprisingcyclopentadiene bonded to a phenyl group via a silicon atom has beenreported to have low catalytic activity in ethylene trimerizationreaction under the same condition as above and to produce a large amountof polyethylene as a by-product (see NON-PATENT DOCUMENT 1).

Moreover, it has been reported that a catalyst system for ethylenetrimerization using a similar half-metallocene titanium complexcomprising cyclopentadiene bonded to a substituted aryl group via acarbon atom exhibits much lower catalytic activity in 1-hexeneproduction and 1-hexene production selectivity under high temperatureconditions of 80° C. than at 30° C. (see NON-PATENT DOCUMENT 2).

An ethylenic copolymer having a main chain with ethylene units and analkyl side chain (e.g., an ethyl or butyl branch), for example, linearlow-density polyethylene, has conventionally been produced bycopolymerizing ethylene and α-olefin (e.g., 1-butene or 1-hexene) in thepresence of an olefin polymerization catalyst.

However, the conventional process for producing an ethylenic copolymerrequires using ethylene and expensive α-olefin as raw material monomersand was thus a less-than-sufficient process economically. Thus, aprocess for producing an ethylenic polymer having an alkyl side chainhas been studied in recent years, which utilizes a tandem polymerizationprocess in which only ethylene is used as the raw material monomer andan ethylene oligomerization catalyst and an olefin copolymerizationcatalyst are used in one reactor.

For example, a process for producing an ethylenic polymer having a butylbranch has been proposed, which comprises polymerizing ethylene in thepresence of an olefin polymerization catalyst obtainable by bringingdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride as an olefin copolymerization catalyst,[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride as anethylene trimerization catalyst, and MMAO as an activating co-catalyticcomponent into contact with each other (see NON-PATENT DOCUMENTS 3 and4). It has been reported therein that an ethylenic polymer having a widerange of melting points and crystallinity is obtained by changing themixing ratio of the olefin copolymerization catalyst and the ethylenetrimerization catalyst and that the ethylenic polymer obtained at 45 to50° C. however has a much lower 1-hexene content than that obtained at25 to 30° C. (see NON-PATENT DOCUMENT 3). It has also been reported thatparticularly at 70° C., the incorporation of 1-hexene is not observedand an ethylene copolymer having a melting point as very high as 133.6°C. is obtained (see NON-PATENT DOCUMENT 4).

NON-PATENT DOCUMENT 4 discloses that an ethylenic polymer having a lowmelting point is obtained by polymerizing ethylene in the presence of anolefin polymerization catalyst obtainable by bringingrac-dimethylsilylenebis(2-methylbenz[e]indenyl)zirconium dichloride asan olefin copolymerization catalyst,[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride as anethylene trimerization catalyst, and MMAO as an activating co-catalyticcomponent into contact with each other. However, no case has reportedpolymerization at a temperature exceeding 25° C.

CITATION LIST

-   PATENT DOCUMENT 1: JP-2004-524959 A-   NON-PATENT DOCUMENT 1: Organometallics 2002, 21, pp 5122-5135.-   NON-PATENT DOCUMENT 2: Chinese Journal of Chemistry 2006, 24, pp    1397-1401.-   NON-PATENT DOCUMENT 3: Macromolecular Rapid Communications 2004, 25,    pp 647-652.-   NON-PATENT DOCUMENT 4: Journal of Polymer Science: Part A: Polymer    Chemistry 2004, 42, pp 4327-4336.

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

Under such circumstances, an object of the present invention is toprovide a transition metal complex that serves as a catalytic componentcapable of efficiently and highly selectively producing 1-hexene throughthe trimerization reaction of ethylene even under high temperatureconditions. Another object of the present invention is to provide aprocess for economically producing an ethylenic polymer having a butylbranch even under high temperature conditions, comprising polymerizingethylene in the presence of an olefin polymerization catalyst obtainableby bringing the transition metal complex used as an ethylenetrimerization catalyst, an olefin copolymerization catalyst and anactivating co-catalytic component into contact with each other.

Means for Solving the Problems

Specifically, a 1st aspect of the present invention relates to atransition metal complex represented by general formula (1):

wherein

M¹ represents a transition metal atom of Group 4 of the Periodic Tableof the Elements; R¹, R², R³ and R⁴ each independently represent

a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R¹, R², R³ and R⁴ is a halogen atom, the alkyl group,the alkoxy group, the aryl group, the aryloxy group, the aralkyl group,the aralkyloxy group, the substituted silyl group or the disubstitutedamino group;R⁵ and R⁹ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 2 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹²s each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁶, R⁷ and R⁸ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R¹⁰ and R¹¹ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;X¹, X² and X³ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;of R¹, R², R³ and R⁴, two groups bonded to two adjacent carbon atoms maybe bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded;of R⁵, R⁶, R⁷, R⁸ and R⁹, two groups bonded to two adjacent carbon atomsmay be bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded; and R¹⁰ and R¹¹ may be bondedto each other to form a ring together with the silicon atom to which R¹⁰and R¹¹ are bonded.

Moreover, a 2nd aspect of the present invention relates to atrimerization catalyst which is obtainable by contacting theabove-mentioned transition metal complex with an activating co-catalyticcomponent.

Furthermore, a 3rd aspect of the present invention relates to a processfor producing 1-hexene using the trimerization catalyst.

Moreover, a 4th aspect of the present invention relates to a process forproducing an ethylenic polymer, comprising polymerizing ethylene in thepresence of an olefin polymerization catalyst obtainable by contacting

a catalytic component for olefin polymerization,a catalytic component for trimerization comprising a transition metalcomplex represented by the following general formula (1), andan activating co-catalytic component:

wherein

M¹ represents a transition metal atom of Group 4 of the Periodic Tableof the Elements; R¹, R², R³ and R⁴ each independently represent

a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹²s each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R¹, R², R³ and R⁴ is a halogen atom, the alkyl group,the alkoxy group, the aryl group, the aryloxy group, the aralkyl group,the aralkyloxy group, the substituted silyl group or the disubstitutedamino group;R⁵ and R⁹ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 2 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁶, R⁷ and R⁸ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R¹⁰ and R¹¹ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;X¹, X² and X³ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹²s each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;of R¹, R², R³ and R⁴, two groups bonded to two adjacent carbon atoms maybe bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded;of R⁵, R⁶, R⁷, R⁸ and R⁹, two groups bonded to two adjacent carbon atomsmay be bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded; and R¹⁰ and R¹¹ may be bondedto each other to form a ring together with the silicon atom to which R¹⁰and R¹¹ are bonded.

Furthermore, a 5th aspect of the present invention relates to a processfor producing the transition metal complex represented by the generalformula (1) or a transition metal complex represented by the followinggeneral formula (1-2) or (1-3):

wherein M¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are asdefined above,R²², R²³ and R²⁴ each independently representa halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent, oran aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, andat least one of R²², R²³ and R²⁴ is the alkyl group, the aryl group orthe aralkyl group; and

wherein M¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are asdefined above,R²⁵, R²⁶ and R²⁷ each independently representa halogen atom,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent, oran aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, andat least one of R²⁵, R²⁶ and R²⁷ is the alkoxy group, the aryloxy groupor the aralkyloxy group.

Moreover, a 6th aspect of the present invention relates to a substitutedcyclopentadiene compound represented by general formula (6-1):

wherein R²⁸, R²⁹, R³⁰ and R³¹ each independently represent

a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R²⁸, R²⁹, R³⁰ and R³¹ is a halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryloxy group, the aralkylgroup, the aralkyloxy group, the substituted silyl group or thedisubstituted amino group;R³² and R³⁶ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R³³, R³⁴ and R³⁵ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R³⁷ representsan alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, ora substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20;R³⁸ representsan alkyl group having 2 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, ora substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20;of R³², R³³, R³⁴, R³⁵ and R³⁶, two groups bonded to two adjacent carbonatoms may be bonded to each other to form a ring together with the twocarbon atoms to which the two groups are bonded;R³⁷ and R³⁸ may be bonded to each other to form a ring together with thesilicon atom to which R³⁷ and R³⁸ are bonded; andthe moiety

represents

a substituted cyclopentadiene compound represented by general formula(6-2):

wherein R³⁹, R⁴⁰, R⁴¹ and R⁴² each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R³⁹, R⁴⁰, R⁴¹ and R⁴² is a halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryloxy group, the aralkylgroup, the aralkyloxy group, the substituted silyl group or thedisubstituted amino group;

R⁴³ and R⁴⁷ each independently represent

a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁴⁴, R⁴⁵ and R⁴⁶ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁴⁸ and R⁴⁹ each independently representan aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent;of R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷, two t groups bonded to two adjacentcarbon atoms may be bonded to each other to form a ring together withthe two carbon atoms to which the two groups are bonded;R⁴⁸ and R⁴⁹ may be bonded to each other to form a ring together with thesilicon atom to which R⁴⁸ and R⁴⁹ are bonded; andthe moiety

represents

a substituted cyclopentadiene compound represented by general formula(6-3):

wherein R⁵⁰, R⁵¹, R⁵² and R⁵³ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹²s each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least two of R⁵⁰, R⁵¹, R⁵² and R⁵³ are the alkyl group;R⁵⁴ and R⁵⁸ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of carbonatoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁵⁵, R⁵⁶ and R⁵⁷ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁵⁹ and R⁶⁰ each independently representan alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, ora substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20;of R⁵⁰, R⁵¹, R⁵², and R⁵³, two of the alkyl groups bonded to twoadjacent carbon atoms are bonded to each other to form a cyclohexenering together with the two carbon atoms to which the two alkyl groupsare bonded;of R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸, two groups bonded to two adjacent carbonatoms may be bonded to each other to form a ring together with the twocarbon atoms to which the two groups are bonded;R⁵⁹ and R⁶⁰ may be bonded to each other to form a ring together with thesilicon atom to which R⁵⁹ and R⁶⁰ are bonded; andthe moiety

represents

a substituted cyclopentadiene compound represented by general formula(6-4):

wherein R⁶¹, R⁶², R⁶³ and R⁶⁴ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R⁶¹, R⁶², R⁶³ and R⁶⁴ is a halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryloxy group, the aralkylgroup, the aralkyloxy group, the substituted silyl group or thedisubstituted amino group;a substructural formula (14)

formed with R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸ and R⁶⁹ is methylphenyl, dimethylphenyl,trimethylphenyl, tetramethylphenyl, pentamethylphenyl, tert-butylphenyl,di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl,anthracene, chlorophenyl, dichlorophenyl, fluorophenyl orbis(trifluoromethyl)phenyl;each of R⁷⁰ and R⁷¹ is a methyl group; andthe moiety

represents

a substituted cyclopentadiene compound represented by general formula(6-5):

wherein R⁷², R⁷³, R⁷⁴ and R⁷⁵ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R⁷², R⁷³, R⁷⁴ and R⁷⁵ is a halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryloxy group, the aralkylgroup, the aralkyloxy group, the substituted silyl group or thedisubstituted amino group;R⁷⁶ and R⁸⁰ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁷⁷, R⁷⁸ and R⁷⁹ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;R⁸¹ represents a methyl group;R⁸² represents an aryl group having 7 to 20 carbon atoms which may havea halogen atom as a substituent;of R⁷⁶, R⁷⁷, R⁷⁸, R⁷⁹ and R⁸⁰, two groups bonded to two adjacent carbonatoms may be bonded to each other to form a ring together with the twocarbon atoms to which the two groups are bonded;R⁸¹ and R⁸² may be bonded to each other to form a ring together with thesilicon atom to which R⁸¹ and R⁸² are bonded; andthe moiety

represents

and

a substituted cyclopentadiene compound represented by general formula(6-6):

wherein R⁸³, R⁸⁴, R⁸⁵ and R⁸⁶ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, andat least one of R⁸³, R⁸⁴, R⁸⁵ and R⁸⁶ is a halogen atom, the alkylgroup, the alkoxy group, the aryl group, the aryloxy group, the aralkylgroup, the aralkyloxy group, the substituted silyl group or thedisubstituted amino group, and not every groups of R⁸³, R⁸⁴, R⁸⁵ and R⁸⁶are a methyl group at the same time;each of R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰ and R⁹¹ is a hydrogen atom;R⁹² and R⁹³ each represent a methyl group; andthe moiety

represents

Moreover, a 7th aspect of the present invention relates to a process forproducing the substituted cyclopentadiene compound represented by any ofthe general formulas (6-1) to (6-6).

Advantages of the Invention

The present invention can provide a transition metal complex that issuitable as a catalytic component capable of efficiently and highlyselectively producing 1-hexene through the trimerization reaction ofethylene even under high temperature conditions. The present inventioncan further provide a process for economically producing an ethylenicpolymer having a butyl branch even under high temperature conditions,comprising polymerizing ethylene in the presence of an olefinpolymerization catalyst obtainable by bringing the transition metalcomplex, which is used as an ethylene trimerization catalyst, an olefincopolymerization catalyst and an activating co-catalyst into contactwith each other.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 graphically represents the time-dependent change of ethyleneabsorption in an embodiment of the present invention.

FIG. 2 graphically represents the time-dependent change of ethyleneabsorption in an embodiment of the present invention.

FIG. 3 graphically represents the time-dependent change of ethyleneabsorption in an embodiment of the present invention.

FIG. 4 graphically represents the time-dependent change of ethyleneabsorption in an embodiment of the present invention.

FIG. 5 graphically represents the time-dependent change of ethyleneabsorption in an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

In the present invention, the term “polymerization” encompasses not onlyhomopolymerization but also copolymerization. Moreover, in the presentinvention, the term “substituent” encompasses a halogen atomconstituting a compound or a group.

Furthermore, in the present invention, substituted cyclopentadienecompounds represented by general formulae (6) and (6-1) to (6-6)respectively have isomers differing in the double bond position of eachcyclopentadienyl ring. In the present invention, the substitutedcyclopentadienyl compounds refer to any of them or a mixture of them.

<Transition Metal Complex (1) (Catalytic Component for Trimerization)>

Hereinafter, the transition metal complex represented by the generalformula (1) will be described in detail.

In the transition metal complex (1), M¹ represents an element of Group 4of the Periodic Table of the Elements, and examples thereof includetitanium, zirconium and hafnium atoms. Among them, a titanium atom ispreferable.

In the transition metal complex (1), the substituents R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, X¹, X² and X³ are as defined above, andspecific examples thereof are shown below.

The halogen atom is a fluorine, chlorine, bromine or iodine atom and ispreferably a chlorine atom.

Specific examples of the “alkyl group having 1 to 20 carbon atoms” inthe alkyl group having 1 to 20 carbon atoms which may have a halogenatom as a substituent include methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl,heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and n-eicosylgroups. Of these, a preferable alkyl group is an alkyl group having 1 to10 carbon atoms, and more preferable examples thereof include methyl,ethyl, isopropyl, tert-butyl and amyl groups. Moreover, the phrase “mayhave a halogen atom as a substituent” in the “alkyl group which may havea halogen atom as a substituent” means that some or all of hydrogenatoms in the alkyl group may be substituted with a halogen atom.Specific examples of the halogen atom are as described above. When thealkyl group has a halogen atom as a substituent, the number of itscarbon atoms is preferably in the range of 1 to 20, more preferably inthe range of 1 to 10. Preferable examples of the alkyl group having ahalogen atom as a substituent can include fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl,perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexylgroups.

Specific examples of the “aryl group having 6 to 20 carbon atoms” in thearyl group having 6 to 20 carbon atoms which may have a halogen atom asa substituent include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups. Of these, apreferable aryl group is an aryl group having 6 to 10 carbon atoms, andmore preferable examples thereof include phenyl group. Moreover, thephrase “may have a halogen atom as a substituent” in the “aryl groupwhich may have a halogen atom as a substituent” means that some or allof hydrogen atoms in the aryl group may be substituted with a halogenatom. Specific examples of the halogen atom are as described above. Whenthe aryl group has a halogen atom as a substituent, the number of itscarbon atoms is preferably in the range of 6 to 20, more preferably inthe range of 6 to 10. Preferable examples of the aryl group having ahalogen atom as a substituent can specifically include fluorophenyl,difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl,chlorophenyl, bromophenyl and iodophenyl groups.

Specific examples of the “aralkyl group having 7 to 20 carbon atoms” inthe aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent include benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl, naphthylmethyl andanthracenylmethyl groups. Of these, a preferable aralkyl group is anaralkyl group having 7 to 10 carbon atoms, and more preferable examplesthereof can include a benzyl group. Moreover, the phrase “may have ahalogen atom as a substituent” in the “aralkyl group which may have ahalogen atom as a substituent” means that some or all of hydrogen atomsin the aralkyl group may be substituted with a halogen atom. Specificexamples of the halogen atom are as described above. When the aralkylgroup has a halogen atom as a substituent, the number of its carbonatoms is preferably in the range of 7 to 20, more preferably in therange of 7 to 10.

Specific examples of the “alkoxy group having 1 to 20 carbon atoms” inthe alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent include methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy,n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy,n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy,heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups. Ofthese, a preferable alkoxy group is an alkoxy group having 1 to 10carbon atoms, and more preferable examples thereof include methoxy,ethoxy and tert-butoxy groups. Moreover, the phrase “may have a halogenatom as a substituent” in the “alkoxy group which may have a halogenatom as a substituent” means that some or all of hydrogen atoms in thealkoxy group may be substituted with a halogen atom. Specific examplesof the halogen atom are as described above. When the alkoxy group has ahalogen atom as a substituent, the number of its carbon atoms ispreferably in the range of 1 to 20, more preferably in the range of 1 to10.

Specific examples of the “alkoxy group having 2 to 20 carbon atoms” inthe alkoxy group having 2 to 20 carbon atoms which may have a halogenatom as a substituent include ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy,n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy,tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy,heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups. Ofthese, a preferable alkoxy group is an alkoxy group having 2 to 10carbon atoms, and more preferable examples thereof include ethoxy andtert-butoxy groups. Moreover, the phrase “may have a halogen atom as asubstituent” in the “alkoxy group which may have a halogen atom as asubstituent” means that some or all of hydrogen atoms in the alkoxygroup may be substituted with a halogen atom. Specific examples of thehalogen atom are as described above. When the alkoxy group has a halogenatom as a substituent, the number of its carbon atoms is preferably inthe range of 2 to 20, more preferably in the range of 2 to 10.

Specific examples of the “aryloxy group having 6 to 20 carbon atoms” inthe aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent include phenoxy, 2-methylphenoxy, 3-methylphenoxy,4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy,2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy,3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy,2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy,3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy,2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy,pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy,n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy,n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy andanthracenoxy groups. Of these, a preferable aryloxy group is an aryloxygroup having 6 to 10 carbon atoms, and more preferable examples thereofinclude phenoxy, 2-methylphenoxy, 3-methylphenoxy and 4-methylphenoxygroups. Moreover, the phrase “may have a halogen atom as a substituent”in the “aryloxy group which may have a halogen atom as a substituent”means that some or all of hydrogen atoms in the aryloxy group may besubstituted with a halogen atom. Specific examples of the halogen atomare as described above. When the aryloxy group has a halogen atom as asubstituent, the number of its carbon atoms is preferably in the rangeof 6 to 20, more preferably in the range of 6 to 10.

Specific examples of the “aralkyloxy group having 7 to 20 carbon atoms”in the aralkyloxy group having 7 to 20 carbon atoms which may have ahalogen atom as a substituent include benzyloxy,(2-methylphenyl)methoxy, (3-methylphenyl)methoxy,(4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy,(2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy,(2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy,(3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy,(2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy,(2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy,(3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy,(2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy,(pentamethylphenyl)methoxy, (ethylphenyl)methoxy,(n-propylphenyl)methoxy, (isopropylphenyl)methoxy,(n-butylphenyl)methoxy, (sec-butylphenyl)methoxy,(tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy,(n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthylmethoxy andanthracenylmethoxy groups. Of these, a preferable aralkyloxy group is anaralkyloxy group having 7 to 10 carbon atoms, and more preferableexamples thereof include benzyloxy group. Moreover, the phrase “may havea halogen atom as a substituent” in the “aralkyloxy group which may havea halogen atom as a substituent” means that some or all of hydrogenatoms in the aralkyloxy group may be substituted with a halogen atom.Specific examples of the halogen atom are as described above. When thearalkyloxy group has a halogen atom as a substituent, the number of itscarbon atoms is preferably in the range of 7 to 20, more preferably inthe range of 7 to 10.

In the substituted silyl group represented by —Si(R¹²)₃, wherein thethree R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, the R¹²groups are each independently a hydrogen atom; a hydrocarbyl group suchas an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl,n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) andan aryl group (e.g., phenyl group); or a halogenated hydrocarbyl groupobtained by substituting some or all of hydrogen atoms in thehydrocarbyl group with a halogen atom, and the total number of carbonatoms in the three R¹² groups is in the range of 1 to 20. The totalnumber of the carbon atoms in the these three R¹² groups is preferablyin the range of 3 to 18. Specific examples of the substituted silylgroup include: monosubstituted silyl groups having one hydrocarbyl orhalogenated hydrocarbyl group, such as methylsilyl, ethylsilyl andphenylsilyl groups, and groups obtained by substituting some or all ofhydrogen atoms in the hydrocarbyl groups of these groups with a halogenatom; disubstituted silyl groups having two hydrocarbyl and/orhalogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl anddiphenylsilyl groups, and groups obtained by substituting some or all ofhydrogen atoms in the hydrocarbyl groups of these groups with a halogenatom; and trisubstituted silyl group having three hydrocarbyl and/orhalogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl,tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups, and groups obtained bysubstituting some or all of hydrogen atoms in the hydrocarbyl groups ofthese groups with a halogen atom. Of these, trisubstituted silyl groupsare preferable, and trimethylsilyl, tert-butyldimethylsilyl andtriphenylsilyl groups, and groups obtained by substituting some or allof hydrogen atoms in these groups with a halogen atom are morepreferable.

In the disubstituted amino group represented by —N(R¹³)₂, wherein thetwo R¹³ groups each independently represent a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the two R¹³ groups is 2 to 20, the R¹³ groups each independentlyrepresent a hydrocarbyl group or a halogenated hydrocarbyl group, andthe total number of the carbon atoms in the two R¹³ groups is in therange of 2 to 20, more preferably in the range of 2 to 10. Thehydrocarbyl group and the halogenated hydrocarbyl group are the same asthose described as the hydrocarbyl group and the halogenated hydrocarbylgroup for the substituted silyl group. Moreover, these two R¹³ groupsmay be bonded to each other to form a ring together with the nitrogenatom to which these two R¹³ groups are bonded. Examples of such adisubstituted amino group include dimethylamino, diethylamino,di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino,di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino,di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino,bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl,pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl anddihydroisoindolyl groups, and groups obtained by substituting some orall of hydrogen atoms in these groups with a halogen atom. Of these,dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, andgroups obtained by substituting some or all of hydrogen atoms in thesegroups with a halogen atom are preferable.

Of R¹, R², R³ and R⁴, two groups bonded to two adjacent carbon atoms maybe bonded to each other to form a ring together with the carbon atoms towhich the two groups are bonded, R¹⁰ and R¹¹ may be bonded to each otherto form a ring together with the silicon atom to which R¹⁰ and R¹¹ arebonded, and of R⁵, R⁶, R⁷, R⁸ and R⁹, two groups bonded to two adjacentcarbon atoms may be bonded to each other to form a ring together withthe carbon atoms to which the two groups are bonded. In this context,the ring is a saturated or unsaturated hydrocarbyl ring substituted witha hydrocarbyl group having 1 to 20 carbon atoms, a saturated orunsaturated silahydrocarbyl ring substituted by a hydrocarbyl grouphaving 1 to 20 carbon atoms, etc. Specific examples thereof includecyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane,cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene,cyclooctane, cyclooctene, benzene, naphthalene, anthracene,silacyclopropane, silacyclobutane, silacyclopropane and silacyclohexanerings.

In the transition metal complex (1), at least one of R¹, R², R³ and R⁴is a substituent other than hydrogen and is preferably a hydrogen atom,a halogen atom, an alkyl group having 1 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms or an aralkyl group having 7 to 20carbon atoms.

Specific examples of R¹, R², R³ and R⁴ are those that can provide acyclopentadienyl 20 substructure represented by substructural formula(15):

wherein R¹, R², R³ and R⁴ are as defined above, and at least one thereofis a substituent other than hydrogen.

For example, the following substructures can be exemplified:

methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl,isopropylcyclopentadienyl, n-butylcyclopentadienyl,sec-butylcyclopentadienyl, tert-butylcyclopentadienyl,dimethylcyclopentadienyl, trimethylcyclopentadienyl,tetramethylcyclopentadienyl, phenylcyclopentadienyl,benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,methyltetrahydroindenyl, dimethyltetrahydroindenyl andoctahydrofluorenyl.

Of the cyclopentadienyl substructures exemplified above, the preferablecyclopentadienyl substructures are tetramethylcyclopentadienyl, etc.

In the transition metal complex (1), R⁵, R⁶, R⁷, R⁸ and R⁹ arepreferably a hydrogen atom, a halogen atom, an alkyl group having 1 to20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkylgroup having 7 to 20 carbon atoms.

Examples of the preferable combination of the moieties represented byR⁵, R⁶, R⁷, R⁸ and R⁹ can include those that can provide the followingsubstructures represented by substructural formula (16):

wherein R⁵, R⁶, R⁷, R⁸ and R⁹ are as defined above.

For example, the following substructures can be exemplified:

phenyl, methylphenyl, dimethylphenyl, trimethylphenyl,tetramethylphenyl, pentamethylphenyl, tert-butylphenyl,di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl,naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl,pentafluorophenyl, bis(trifluoromethyl)phenyl and methoxyphenyl.

Of the substructures exemplified above, the preferable substructures arephenyl, methylphenyl, dimethylphenyl, trimethylphenyl, etc.

In the transition metal complex (1), R¹⁰ and R¹¹ are preferably ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbonatoms, and specific examples thereof include methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, 4-methylphenyl,3-methylphenyl, 2-methylphenyl, naphthyl and benzyl group.

Examples of a preferable combination of the moieties represented by R¹⁰and R¹¹ can include those that can provide the following substructuresrepresented by substructural formula (17):

wherein R¹⁰ and R¹¹ are as defined above:

For example, the following substructures can be exemplified:

dimethylsilylene, diethylsilylene, ethylmethylsilylene,di(n-propyl)silylene, methyl(n-propyl)silylene, di(n-butyl)silylene,n-butylmethylsilylene, n-hexylmethylsilylene, methyl(n-octyl)silylene,n-decylmethylsilylene, methyl(n-octadecyl)silylene,cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilyleneand methylphenylsilylene.

Preferable examples thereof can include a substructure represented bythe substructural formula (17), wherein

R¹⁰ is a methyl group, and R¹¹ isan alkyl group having 2 to 20 carbon atoms which may have a halogen atomas a substituent, oran aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent; orR¹⁰ and R¹¹ are the same and representan alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent, oran aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent.

Specifically, the substructure can be dimethylsilylene, diethylsilylene,ethylmethylsilylene, n-butylmethylsilylene, cyclohexylmethylsilylene,cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene,etc.

Preferable examples of the transition metal complex of the formula (1)can include transition metal complexes, wherein R⁶ and R⁸ are

an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent, oran aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent, and

R¹⁰ and R¹¹ are

an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent.

Specific examples of the transition metal complex (1) can include thefollowing complexes:

titanium chloride complexes such as[1-dimethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,[1-dimethylphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,[1-dimethylphenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-dimethylphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-dimethylphenylsilyl-indenyl]titanium trichloride,[1-dimethylphenylsilyl-2-methylindenyl]titanium trichloride,[9-dimethylphenylsilyl-fluorenyl]titanium trichloride,[1-dimethylphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-dimethylphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,[9-dimethylphenylsilyl-octahydrofluorenyl]titanium trichloride,

[1-diethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,[1-diethylphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,[1-diethylphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,[1-diethylphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride,[1-diethylphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride,[1-diethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-diethylphenylsilyl-indenyl]titanium trichloride,[1-diethylphenylsilyl-2-methylindenyl]titanium trichloride,[9-diethylphenylsilyl-fluorenyl]titanium trichloride,[1-diethylphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-diethylphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,[9-diethylphenylsilyl-octahydrofluorenyl]titanium trichloride,

[1-cyclotetramethylene(phenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-cyclotetramethylene(phenyl)silyl-indenyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-cyclotetramethylene(phenyl)silyl-fluorenyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-cyclotetramethylene(phenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-ethylmethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,[1-ethylmethylphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,[1-ethylmethylphenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-ethylmethylphenylsilyl-indenyl]titanium trichloride,[1-ethylmethylphenylsilyl-2-methylindenyl]titanium trichloride,[9-ethylmethylphenylsilyl-fluorenyl]titanium trichloride,[1-ethylmethylphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-ethylmethylphenylsilyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-ethylmethylphenylsilyl-octahydrofluorenyl]titaniumtrichloride,

[1-n-butylmethylphenylsilyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-n-butylmethylphenylsilyl-indenyl]titanium trichloride,[1-n-butylmethylphenylsilyl-2-methylindenyl]titanium trichloride,[9-n-butylmethylphenylsilyl-fluorenyl]titanium trichloride,[1-n-butylmethylphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-n-butylmethylphenylsilyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-n-butylmethylphenylsilyl-octahydrofluorenyl]titaniumtrichloride,

[1-methyldiphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,[1-methyldiphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,[1-methyldiphenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-methyldiphenylsilyl-indenyl]titanium trichloride,[1-methyldiphenylsilyl-2-methylindenyl]titanium trichloride,[9-methyldiphenylsilyl-fluorenyl]titanium trichloride,[1-methyldiphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-methyldiphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,[9-methyldiphenylsilyl-octahydrofluorenyl]titanium trichloride,

[1-methylbis(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-methylbis(3,5-dimethylphenyl)silyl-indenyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-methylbis(3,5-dimethylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-methylbis(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-methylbis(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-cyclohexylmethylphenylsilyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-cyclohexylmethylphenylsilyl-indenyl]titaniumtrichloride, [1-cyclohexylmethylphenylsilyl-2-methylindenyl]titaniumtrichloride, [9-cyclohexylmethylphenylsilyl-fluorenyl]titaniumtrichloride, [1-cyclohexylmethylphenylsilyl-tetrahydroindenyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-cyclohexylmethylphenylsilyl-octahydrofluorenyl]titaniumtrichloride,

[1-methyl(n-octadecyl)phenylsilyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-methyl(n-octadecyl)phenylsilyl-indenyl]titaniumtrichloride, [1-methyl(n-octadecyl)phenylsilyl-2-methylindenyl]titaniumtrichloride, [9-methyl(n-octadecyl)phenylsilyl-fluorenyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-tetrahydroindenyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-methyl(n-octadecyl)phenylsilyl-octahydrofluorenyl]titaniumtrichloride,

[1-triphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-ethylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-ethylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-n-propylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-n-propylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-isopropylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-isopropylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-n-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-n-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-sec-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-sec-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-tert-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-tert-butylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-phenylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-phenylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-2-benzylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-triphenylsilyl-indenyl]titanium trichloride,[1-triphenylsilyl-2-methylindenyl]titanium trichloride,[9-triphenylsilyl-fluorenyl]titanium trichloride,[1-triphenylsilyl-tetrahydroindenyl]titanium trichloride,[1-triphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,[9-triphenylsilyl-octahydrofluorenyl]titanium trichloride,

[1-tri(4-n-butylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tri(4-n-butylphenyl)silyl-indenyl]titanium trichloride,[1-tri(4-n-butylphenyl)silyl-2-methylindenyl]titanium trichloride,[9-tri(4-n-butylphenyl)silyl-fluorenyl]titanium trichloride,[1-tri(4-n-butylphenyl)silyl-tetrahydroindenyl]titanium trichloride,[1-tri(4-n-butylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-tri(4-n-butylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tri(3-methylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-(3-methylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tri(3-methylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tri(3-methylphenyl)silyl-indenyl]titanium trichloride,[1-tri(3-methylphenyl)silyl-2-methylindenyl]titanium trichloride,[9-tri(3-methylphenyl)silyl-fluorenyl]titanium trichloride,[1-tri(3-methylphenyl)silyl-tetrahydroindenyl]titanium trichloride,[1-tri(3-methylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-tri(3-methylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tri(3-isopropylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-(3-isopropylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tri(3-isopropylphenyl)silyl-indenyl]titaniumtrichloride, [1-tri(3-isopropylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tri(3-isopropylphenyl)silyl-fluorenyl]titaniumtrichloride, [1-tri(3-isopropylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tri(3-isopropylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-tri(3-isopropylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-dimethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-dimethyl(3,5-dimethylphenyl)silyl-indenyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-dimethyl(3,5-dimethylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-dimethyl(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-dimethyl(3,5-di-n-hexylphenyl)silyl-indenyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-dimethyl(3,5-di-n-hexylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-dimethyl(3,5-di-n-hexylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-n-butylmethyl(3,5-dimethylphenyl)silyl-indenyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methylindenyl]titaniumtrichloride,[9-n-butylmethyl(3,5-dimethylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-n-butylmethyl(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tris(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tris(3,5-dimethylphenyl)silyl-indenyl]titaniumtrichloride, [1-tris(3,5-dimethylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tris(3,5-dimethylphenyl)silyl-fluorenyl]titaniumtrichloride, [1-tris(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-tris(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tris(3,5-diethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tris(3,5-diethylphenyl)silyl-indenyl]titaniumtrichloride, [1-tris(3,5-diethylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tris(3,5-diethylphenyl)silyl-fluorenyl]titaniumtrichloride, [1-tris(3,5-diethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tris(3,5-diethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride, [9-tris(3,5-diethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tris(3,5-diisopropylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tris(3,5-diisopropylphenyl)silyl-indenyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tris(3,5-diisopropylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tris(3,5-diisopropylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-tris(3,5-diisopropylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tris(3,5-di-tert-butylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2,3,5-timethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-etylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-etylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tris(3,5-di-tert-butylphenyl)silyl-indenyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tris(3,5-di-tert-butylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tris(3,5-di-tert-butylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-tris(3,5-di-tert-butylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-tris(3,5-di-n-hexylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-tris(3,5-di-n-hexylphenyl)silyl-indenyl]titaniumtrichloride, [1-tris(3,5-di-n-hexylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-tris(3,5-di-n-hexylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-tris(3,5-di-n-hexylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-tris(3,5-di-n-hexylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl)-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-indenyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-methylindenyl]titaniumtrichloride,[9-n-butylmethyl(2,4,6-trimethylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride,[9-n-butylmethyl(2,4,6-trimethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride,

[1-n-butylmethyl(pentamethylphenyl)silyl-2-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-methylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-ethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-n-propylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-isopropylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-n-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-sec-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-tert-butylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-phenylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-benzylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-3-benzylcyclopentadienyl]titaniumtrichloride, [1-n-butylmethyl(pentamethylphenyl)silyl-indenyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-methylindenyl]titaniumtrichloride, [9-n-butylmethyl(pentamethylphenyl)silyl-fluorenyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-tetrahydroindenyl]titaniumtrichloride,[1-n-butylmethyl(pentamethylphenyl)silyl-2-methyltetrahydroindenyl]titaniumtrichloride and[9-n-butylmethyl(pentamethylphenyl)silyl-octahydrofluorenyl]titaniumtrichloride.

Moreover, examples of the transition metal complex (1) also include:transition metal chloride complexes such as zirconium chloride complexesin which “titanium” in the complexes exemplified above is replaced with“zirconium”, and hafnium chloride complexes in which “titanium” isreplaced with “hafnium”; titanium halide complexes such as titaniumfluoride complexes in which “chloride” in the complexes are replacedwith “fluoride”, titanium bromide complexes in which “chloride” isreplaced with “bromide” and titanium iodide complexes in which“chloride” is replaced with “iodide”; titanium hydride complexes inwhich “chloride” is replaced with “hydride”; alkylated titaniumcomplexes such as a methylated titanium complex in which “chloride” isreplaced with “methyl”; arylated titanium complexes such as a phenylatedtitanium complex in which “chloride” is replaced with “phenyl”;aralkylated titanium complexes such as a benzylated titanium complex inwhich “chloride” is replaced with “benzyl”; titanium alkoxide complexessuch as a titanium methoxide complex in which “chloride” is replacedwith “methoxide”, a titanium n-butoxide complex in which “chloride” isreplaced with “n-butoxide” and a titanium isopropoxide complex in which“chloride” is replaced with “isopropoxide”; titanium aryloxide complexessuch as a titanium phenoxide complex in which “chloride” is replacedwith “phenoxide”; titanium aralkyloxide complexes such as a titaniumbenzyloxide complex in which “chloride” is replaced with “benzyloxide”;and titanium amide complexes such as a titanium dimethylamide complex inwhich “chloride” is replaced with “dimethylamide” and a titaniumdiethylamide complex in which “chloride” is replaced with“diethylamide”. Of these, alkylated titanium complexes are preferable,and trimethyl titanium complexes are more preferable.

Preferable examples of the transition metal complex of formula (1)include[1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-cyclotetramethylene(phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride and[1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride. More preferable examples thereof include[1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride,[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride and[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride.

<Process for Producing Transition Metal Complex (1)>

The transition metal complex (1) can be produced by, for example, aproduction process comprising the steps of:

reacting a substituted cyclopentadiene compound represented by a formula(6) (hereinafter, referred to as a “substituted cyclopentadiene compound(6)”) with a base in the presence of an amine compound:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are as definedabove; andreacting the reaction product of the substituted cyclopentadienecompound (6) and the base with a transition metal compound representedby the following general formula (7) (hereinafter, referred to as a“transition metal compound (7)”):

wherein M¹, X¹, X² and X³ are as defined above, X¹² independently ateach occurrence represent a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, and m represents 0 or 1.

Hereinafter, the step of reacting a substituted cyclopentadiene compound(6) with a base in the presence of an amine compound may be referred toas a “1st reaction step”, and the step of reacting the reaction productof the substituted cyclopentadiene compound (6) and the base with atransition metal compound (7) may be referred to as a “2nd reactionstep”.

Isomers of the substituted cyclopentadiene compound (6), differing inthe double bond position of the cyclopentadiene ring include thefollowing structural isomers:

The compound represented by the general formula (6) has isomersdiffering in the double bond position of each cyclopentadienyl ring. Inthe present invention, it represents any of them or a mixture of them.

In the transition metal compound (7), the substituent X¹² is as definedabove, and specific examples thereof can include the same as thoseexemplified for X¹, X² and X³.

Examples of the transition metal compound (7) include: titanium halidessuch as titanium tetrachloride, titanium trichloride, titaniumtetrabromide and titanium tetraiodide; titanium amidoes such astetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium,trichloro(dimethylamino)titanium and tetrakis(diethylamino)titanium; andtitanium alkoxides titanium such as tetraisopropoxytitanium,tetra-n-butoxytitanium, dichlorodiisopropoxytitanium andtrichloroisopropoxytitanium. Moreover, examples of the transition metalcompound (7) include compounds in which “titanium” in any of thesecompounds is replaced with “zirconium” or “hafnium”. Of them, apreferable transition metal compound (7) is titanium tetrachloride.

Examples of the base reacted with the substituted cyclopentadienecompound (6) in the 1st reaction step include organic alkali metalcompounds typified by organic lithium compounds such as methyllithium,ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium,lithiumtrimethylsilyl acetylide, lithium acetylide,trimethylsilylmethyllithium, vinyllithium, phenyllithium andallyllithium.

The amount of the base used may be in the range of 0.5 to 5 moles perone mole of the substituted cyclopentadienyl compound (6).

In the reaction of the substituted cyclopentadiene compound (6) with thebase in the 1st reaction step, an amine compound is used together withthe organic alkali metal compound. Examples of such an amine compoundinclude: primary amine compounds such as methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, tert-butylamine,n-octylamine, n-decylamine, aniline and ethylenediamine; secondary aminecompounds such as dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine,di-n-decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine;and tertiary amine compounds such as trimethylamine, triethylamine,tri-n-propylamine, tri-n-butylamine, diisopropylethylamine,tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline,N,N,N′,N′-tetramethylethylenediamine, N-methylpyrrolidine and4-dimethylaminopyridine. The amount of such an amine compound used ispreferably 10 moles or smaller, more preferably in the range of 0.5 to10 moles, even more preferably in the range of 1 to 5 moles, per onemole of the organic alkali metal compound.

In the 1st reaction step, the reaction of the substitutedcyclopentadiene compound (6) with the base is preferably performed inthe presence of a solvent. Moreover, when the solvent is used, thesubstituted cyclopentadiene compound (6) and the base are reacted in thesolvent and then a transition metal compound (7) can be added into thisreaction mixture to thereby further react the transition metal compound(7) with the reaction product of the substituted cyclopentadienecompound (6) and the base. Solids may be deposited in the reactionmixture obtained by reacting the substituted cyclopentadiene compound(6) and the base. In this case, the solvent may be further added untilthe deposited solid is dissolved; or the deposited solid may betemporarily separated by filtration or the like, and the solvent may beadded to the separated solid for dissolution or suspension, followed bythe addition of a transition metal compound (7). When the solvent isused, the substituted cyclopentadiene compound (6), the base and thetransition metal compound (7) can also be added simultaneously to thesolvent to thereby perform the 1st reaction step and the 2nd reactionstep almost simultaneously.

The solvent used in the 1st reaction step or in the 1st and 2nd reactionsteps is an inert solvent that does not significantly hinder theprogress of the reaction associated with these steps. Examples of such asolvent include aprotic solvents such as: aromatic hydrocarbyl solventssuch as benzene and toluene; aliphatic hydrocarbyl solvents such ashexane and heptane; ether solvents such as diethyl ether,tetrahydrofuran and 1,4-dioxane; amide solvents such ashexamethylphosphoric amide and dimethylformamide; polar solvents such asacetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutylketone and cyclohexanone; and halogenic solvents such asdichloromethane, dichloroethane, chlorobenzene and dichlorobenzene.These solvents can be used alone or as a mixture of two or more thereof,and the amount thereof used is preferably 1 to 200 parts by weight, morepreferably 3 to 50 parts by weight, per one part by weight of thesubstituted cyclopentadiene compound (6).

The amount of the transition metal compound (7) used is preferably inthe range of 0.5 to 3 moles, more preferably in the range of 0.7 to 1.5moles, per one mole of the substituted cyclopentadiene compound (6).

The reaction temperature in the 1st and 2nd reaction steps needs only tobe a temperature not less than −100° C. and not more than the boilingpoint of the solvent and is preferably in the range of −80 to 100° C.

From the reaction mixture thus obtained through the 1st and 2nd reactionsteps, the produced transition metal complex (1) can be taken out byvarious purification methods known in the art. For example, thetransition metal complex (1) of interest can be obtained by a method inwhich after the 1st and 2nd reaction steps, the formed precipitates arefiltered off, and the filtrate is concentrated to deposit a transitionmetal complex, which is then collected by filtration.

<Method for Producing Transition Metal Complex (1-2)>

The transition metal complex (1-2) can be produced, for example, byreacting a transition metal halide complex represented by generalformula (I-1):

wherein M¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are asdefined above, andX¹³, X¹⁴ and X¹⁵ are a halogen atom,with an alkali metal compound represented by a formula (8):

M⁶-R²⁰  (8)

wherein M⁶ represents an alkali metal, and R²⁰ representsan alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent, oran aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent, oran alkaline earth metal compound represented by a formula (9):

wherein M⁷ represents an alkaline earth metal, R²¹ representsan alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent, oran aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,X¹⁶ represents a halogen atom, r is 1 or 2, and the total sum of r and sis 2.

Examples of the transition metal complex (1-2) include alkylatedtitanium, arylated titanium and aralkylated titanium complexes.

In the transition metal complex (1-2), the substituents R²², R²³ and R²⁴are as defined above, and specific examples thereof can include the sameas those exemplified for R¹.

Examples of the transition metal halide complex (1-1) include titaniumchloride, titanium fluoride, titanium bromide and titanium iodidecomplexes.

In the transition metal compound (1-1), the substituents X¹³, X¹⁴ andX¹⁵ are as defined above, and specific examples thereof can include thesame as those exemplified for X¹, X² and X³

In the alkali metal compound (8), M⁶ represents an alkali metal of thePeriodic Table of the Elements, and examples thereof include lithium,sodium and potassium atoms. Among them, lithium and sodium atoms arepreferable, and a lithium atom is particularly preferable.

In the alkali metal compound (8), the substituent R²⁰ is as definedabove, and specific examples thereof can include the same as thoseexemplified for R¹.

In the alkaline earth metal compound (9), M⁷ represents an alkalineearth metal of the Periodic Table of the Elements, and examples thereofinclude magnesium, calcium and strontium atoms. Among them, a magnesiumatom is preferable.

In the alkaline earth metal compound (9), the substituent R²¹ is asdefined above, and specific examples thereof can include the same asthose exemplified for R¹.

In the alkaline earth metal compound (9), the substituent X¹⁶ is asdefined above, and specific examples thereof can include the same asthose exemplified for X¹, X² and X³.

In the alkaline earth metal compound (9), r is 1 or 2, and the total sumof r and s is 2.

Examples of the alkali metal compound (8) include: alkyllithiums such asmethyllithium, ethyllithium, n-propyllithium, isopropyllithium,n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium,neopentyllithium, amyllithium, n-hexyllithium, n-octyllithium,n-decyllithium, n-dodecyllithium, n-pentadecyllithium andn-eicosyllithium;

aralkyllithiums such as benzyllithium, (2-methylphenyl)methyllithium,(3-methylphenyl)methyllithium, (4-methylphenyl)methyllithium,(2,3-dimethylphenyl)methyllithium, (2,4-dimethylphenyl)methyllithium,(2,5-dimethylphenyl)methyllithium, (2,6-dimethylphenyl)methyllithium,(3,4-dimethylphenyl)methyllithium, (2,3,4-trimethylphenyl)methyllithium,(2,3,5-trimethylphenyl)methyllithium,(2,3,6-trimethylphenyl)methyllithium,(3,4,5-trimethylphenyl)methyllithium,(2,4,6-trimethylphenyl)methyllithium,(2,3,4,5-tetramethylphenyl)methyllithium,(2,3,4,6-tetramethylphenyl)methyllithium,(2,3,5,6-tetramethylphenyl)methyllithium,(pentamethylphenyl)methyllithium, (ethylphenyl)methyllithium,(n-propylphenyl)methyllithium, (isopropylphenyl)methyllithium,(n-butylphenyl)methyllithium, (sec-butylphenyl)methyllithium,(tert-butylphenyl)methyllithium, (n-pentylphenyl)methyllithium,(neopentylphenyl)methyllithium, (n-hexylphenyl)methyllithium,(n-octylphenyl)methyllithium, (n-decylphenyl)methyllithium,(n-dodecylphenyl)methyllithium, (n-tetradecylphenyl)methyllithium,naphthylmethyllithium and anthracenylmethyllithium; and

aryllithiums such as phenyllithium, 2-tolyllithium, 3-tolyllithium,4-tolyllithium, 2,3-xylyllithium, 2,4-xylyllithium, 2,5-xylyllithium,2,6-xylyllithium, 3,4-xylyllithium, 3,5-xylyllithium,2,3,4-trimethylphenyllithium, 2,3,5-trimethylphenyllithium,2,3,6-trimethylphenyllithium, 2,4,6-trimethylphenyllithium,3,4,5-trimethylphenyllithium, 2,3,4,5-tetramethylphenyllithium,2,3,4,6-tetramethylphenyllithium, 2,3,5,6-tetramethylphenyllithium,pentamethylphenyllithium, ethylphenyllithium, n-propylphenyllithium,isopropylphenyllithium, n-butylphenyllithium, sec-butylphenyllithium,tert-butylphenyllithium, n-pentylphenyllithium, neopentylphenyllithium,n-hexylphenyllithium, n-octylphenyllithium, n-decylphenyllithium,n-dodecylphenyllithium, n-tetradecylphenyllithium, naphthyllithium andanthracenyllithium. Methyllithium, benzyllithium and phenyllithium arepreferable.

The amount of the alkali metal compound (8) used is usually in the rangeof 2- to 10-fold by mol, preferably in the range of 1- to 3-fold by mol,with respect to the transition metal halide complex (1-1).

Examples of the alkaline earth metal compound (9) include:dialkylmagnesiums and asymmetric dialkylmagnesiums such asdimethylmagnesium, diethylmagnesium, di-n-propylmagnesium,diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium,di-tert-butylmagnesium, di-n-pentylmagnesium, di-neopentylmagnesium,diamylmagnesium, di-n-hexylmagnesium, di-n-octylmagnesium,di-n-decylmagnesium, di-n-dodecylmagnesium, di-n-pentadecylmagnesium anddi-n-eicosylmagnesium;

diaralkylmagnesiums and asymmetric diaralkylmagnesiums such asdibenzylmagnesium, di-(2-methylphenyl)methylmagnesium,di-(3-methylphenyl)methylmagnesium, di-(4-methylphenyl)methylmagnesium,di-(2,3-dimethylphenyl)methylmagnesium,di-(2,4-dimethylphenyl)methylmagnesium,di-(2,5-dimethylphenyl)methylmagnesium,di-(2,6-dimethylphenyl)methylmagnesium,di-(3,4-dimethylphenyl)methylmagnesium,di-(2,3,4-trimethylphenyl)methylmagnesium,di-(2,3,5-trimethylphenyl)methylmagnesium,di-(2,3,6-trimethylphenyl)methylmagnesium,di-(3,4,5-trimethylphenyl)methylmagnesium,di-(2,4,6-trimethylphenyl)methylmagnesium,di-(2,3,4,5-tetramethylphenyl)methylmagnesium,di-(2,3,4,6-tetramethylphenyl)methylmagnesium,di-(2,3,5,6-tetramethylphenyl)methylmagnesium,di-(pentamethylphenyl)methylmagnesium, di-(ethylphenyl)methylmagnesium,di-(n-propylphenyl)methylmagnesium, di-(isopropylphenyl)methylmagnesium,di-(n-butylphenyl)methylmagnesium, di-(sec-butylphenyl)methylmagnesium,di-(tert-butylphenyl)methylmagnesium,di-(n-pentylphenyl)methylmagnesium, di-(neopentylphenyl)methylmagnesium,di-(n-hexylphenyl)methylmagnesium, di-(n-octylphenyl)methylmagnesium,di-(n-decylphenyl)methylmagnesium, di-(n-dodecylphenyl)methylmagnesium,di-(n-tetradecylphenyl)methylmagnesium, dinaphthylmethylmagnesium anddianthracenylmethylmagnesium;

diarylmagnesiums and asymmetric diarylmagnesiums such asdiphenylmagnesium, di-2-tolylmagnesium, di-3-tolylmagnesium,di-4-tolylmagnesium, di-2,3-xylylmagnesium, di-2,4-xylylmagnesium,di-2,5-xylylmagnesium, di-2,6-xylylmagnesium, di-3,4-xylylmagnesium,di-3,5-xylylmagnesium, di-2,3,4-trimethylphenylmagnesium,di-2,3,5-trimethylphenylmagnesium, di-2,3,6-trimethylphenylmagnesium,di-2,4,6-trimethylphenylmagnesium, di-3,4,5-trimethylphenylmagnesium,di-2,3,4,5-tetramethylphenylmagnesium,di-2,3,4,6-tetramethylphenylmagnesium,di-2,3,5,6-tetramethylphenylmagnesium, di-pentamethylphenylmagnesium,di-ethylphenylmagnesium, di-n-propylphenylmagnesium,di-isopropylphenylmagnesium, di-n-butylphenylmagnesium,di-sec-butylphenylmagnesium, di-tert-butylphenylmagnesium,di-n-pentylphenylmagnesium, di-neopentylphenylmagnesium,di-n-hexylphenylmagnesium, di-n-octylphenylmagnesium,di-n-decylphenylmagnesium, di-n-dodecylphenylmagnesium,di-n-tetradecylphenylmagnesium, dinaphthylmagnesium anddianthracenylmagnesium;

asymmetric organic magnesium compounds such as alkylaralkylmagnesiums,alkylarylmagnesiums and aralkylarylmagnesiums;

alkylmagnesium chlorides such as methylmagnesium chloride,ethylmagnesium chloride, n-propylmagnesium chloride, isopropylmagnesiumchloride, n-butylmagnesium chloride, sec-butylmagnesium chloride,tert-butylmagnesium chloride, n-pentylmagnesium chloride,neopentylmagnesium chloride, amylmagnesium chloride, n-hexylmagnesiumchloride, n-octylmagnesium chloride, n-decylmagnesium chloride,n-dodecylmagnesium chloride, n-pentadecylmagnesium chloride andn-eicosylmagnesium chloride;

aralkylmagnesium chlorides such as benzylmagnesium chloride,(2-methylphenyl)methylmagnesium chloride,(3-methylphenyl)methylmagnesium chloride,(4-methylphenyl)methylmagnesium chloride,(2,3-dimethylphenyl)methylmagnesium chloride,(2,4-dimethylphenyl)methylmagnesium chloride,(2,5-dimethylphenyl)methylmagnesium chloride,(2,6-dimethylphenyl)methylmagnesium chloride,(3,4-dimethylphenyl)methylmagnesium chloride,(2,3,4-trimethylphenyl)methylmagnesium chloride,(2,3,5-trimethylphenyl)methylmagnesium chloride,(2,3,6-trimethylphenyl)methylmagnesium chloride,(3,4,5-trimethylphenyl)methylmagnesium chloride,(2,4,6-trimethylphenyl)methylmagnesium chloride,(2,3,4,5-tetramethylphenyl)methylmagnesium chloride,(2,3,4,6-tetramethylphenyl)methylmagnesium chloride,(2,3,5,6-tetramethylphenyl)methylmagnesium chloride,(pentamethylphenyl)methylmagnesium chloride,(ethylphenyl)methylmagnesium chloride, (n-propylphenyl)methylmagnesiumchloride, (isopropylphenyl)methylmagnesium chloride,(n-butylphenyl)methylmagnesium chloride,(sec-butylphenyl)methylmagnesium chloride,(tert-butylphenyl)methylmagnesium chloride,(n-pentylphenyl)methylmagnesium chloride,(neopentylphenyl)methylmagnesium chloride,(n-hexylphenyl)methylmagnesium chloride, (n-octylphenyl)methylmagnesiumchloride, (n-decylphenyl)methylmagnesium chloride,(n-dodecylphenyl)methylmagnesium chloride,(n-tetradecylphenyl)methylmagnesium chloride, naphthylmethylmagnesiumchloride and anthracenylmethylmagnesium chloride;

arylmagnesium chlorides such as phenylmagnesium chloride,2-tolylmagnesium chloride, 3-tolylmagnesium chloride, 4-tolylmagnesiumchloride, 2,3-xylylmagnesium chloride, 2,4-xylylmagnesium chloride,2,5-xylylmagnesium chloride, 2,6-xylylmagnesium chloride,3,4-xylylmagnesium chloride, 3,5-xylylmagnesium chloride,2,3,4-trimethylphenylmagnesium chloride, 2,3,5-trimethylphenylmagnesiumchloride, 2,3,6-trimethylphenylmagnesium chloride,2,4,6-trimethylphenylmagnesium chloride, 3,4,5-trimethylphenylmagnesiumchloride, 2,3,4,5-tetramethylphenylmagnesium chloride,2,3,4,6-tetramethylphenylmagnesium chloride,2,3,5,6-tetramethylphenylmagnesium chloride, pentamethylphenylmagnesiumchloride, ethylphenylmagnesium chloride, n-propylphenylmagnesiumchloride, isopropylphenylmagnesium chloride, n-butylphenylmagnesiumchloride, sec-butylphenylmagnesium chloride, tert-butylphenylmagnesiumchloride, n-pentylphenylmagnesium chloride, neopentylphenylmagnesiumchloride, n-hexylphenylmagnesium chloride, n-octylphenylmagnesiumchloride, n-decylphenylmagnesium chloride, n-dodecylphenylmagnesiumchloride, n-tetradecylphenylmagnesium chloride, naphthylmagnesiumchloride and anthracenylmagnesium chloride; and compounds in whichchloride is replaced with bromide or iodide in these compounds.Preferable examples thereof include dimethylmagnesium,dibenzylmagnesium, diphenylmagnesium, methylmagnesium bromide,benzylmagnesium bromide phenylmagnesium bromide, and so on.

The amount of the alkaline earth metal compound (9) used is usually inthe range of 1- to 10-fold by mol, preferably in the range of 1- to3-fold by mol, with respect to the transition metal halide complex(1-1).

The reaction method is not particularly limited, and the reaction isusually preferably performed by adding the organic alkali metal oralkaline earth metal compound to the transition metal halide complex(1-1) in the presence of a solvent in an inert atmosphere of nitrogen,argon, or the like.

Examples of the solvent for the reaction can include: aliphatichydrocarbyl solvents such as pentane, hexane, cyclohexane, heptane andoctane; aromatic hydrocarbyl solvents such as benzene, toluene, xylene,mesitylene and ethylbenzene; halogenated hydrocarbyl solvents such aschloroform, methylene dichloride, monochlorobenzene and dichlorobenzene;and ethers such as diethyl ether, dibutyl ether, methyl-t-butyl etherand tetrahydrofuran. These solvents are used alone or as a mixture oftwo or more thereof, and the amount thereof used is usually in the rangeof 1- to 200-fold by weight, preferably in the range of 3- to 30-fold byweight, with respect to the transition metal halide complex (1-1).

The temperature of the reaction is usually −100° C. to the boiling pointof the solvent, preferably −80° C. to 30° C. The reaction time is notparticularly limited. After the completion of the reaction, for example,insoluble matter is filtered off, and the filtrate is then concentratedto obtain a crystal, which can then be collected by filtration to obtainthe transition metal complex (1-2) of interest.

<Method for Producing Transition Metal Complex (1-3)>

The transition metal complex (1-3) can be produced, for example, byreacting a transition metal halide complex represented by generalformula (I-1):

wherein M¹, R¹, R², R³, R⁴R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, X¹³, X¹⁴ and X¹⁵are as defined above, with an alkali metal compound represented bygeneral formula (10):

M⁶-OR²⁰  (10)

wherein M⁶ and R²⁰ are as defined above, oran alkaline earth metal compound represented by formula (11):

wherein M⁷, R²¹, X¹⁶, r and s are as defined above.

Examples of the transition metal complex (1-3) include titaniumalkoxide, titanium aryloxide and titanium aralkyloxide complexes.

In the transition metal complex (1-3), the substituents R²⁵, R²⁶ and R²⁷are as defined above, and specific examples thereof can include the sameas those exemplified for R¹.

Examples of the transition metal halide complex (1-1) include titaniumchloride, titanium fluoride, titanium bromide and titanium iodidecomplexes.

In the transition metal compound (1-1), the substituents X¹³, X¹⁴ andX¹⁵ are as defined above, and specific examples thereof can include thesame as those exemplified for X¹, X² and X³

In the alkali metal compound (10), M⁶ represents an alkali metal of thePeriodic Table of the Elements, and examples thereof include lithium,sodium and potassium atoms. Among them, lithium and sodium atoms arepreferable, and a lithium atom is particularly preferable.

In the alkali metal compound (10), the substituent R²⁰ is as definedabove, and specific examples thereof can include the same as thoseexemplified for R¹.

In the alkaline earth metal compound (II), M⁷ represents an alkalineearth metal of the Periodic Table of the Elements, and examples thereofinclude magnesium, calcium and strontium atoms. Among them, a magnesiumatom is preferable.

In the alkaline earth metal compound (II), the substituent R²¹ is asdefined above, and specific examples thereof can include the same asthose exemplified for R¹.

In the alkaline earth metal compound (II), the substituent X¹⁶ is asdefined above, and specific examples thereof can include the same asthose exemplified for X¹, X² and X³.

In the alkaline earth metal compound (II), r is 1 or 2, and the totalsum of r and s is 2.

The transition metal complex (1-3) can be produced by a process in whichthe alkali metal compound (10) is allowed to act on the transition metalcomplex (1-1) (hereinafter, referred to as process A-1) or by a processin which the alkaline earth metal compound (II) is allowed to actthereon (hereinafter, referred to as process A-2).

Moreover, the transition metal complex (1-3) can also be produced by aprocess in which an alcohol compound is allowed to act on the transitionmetal complex (1-1) in the presence of a base (hereinafter, referred toas process B).

Examples of the alkali metal compound represented by the general formula(10) include: sodium methoxide, sodium ethoxide, sodium n-propoxide,sodium isopropoxide, sodium n-butoxide, sodium sec-butoxide, sodiumtert-butoxide, sodium n-pentoxide, sodium neopentoxide, sodiummethoxyethoxide, sodium ethoxyethoxide, sodium benzyloxide, sodium1-phenylethoxide, and alkali metal alkoxides derived from monools, inwhich sodium is replaced with lithium or potassium in these compounds;

lithium phenoxide, lithium 2-methylphenoxide, lithium 3-methylphenoxide,lithium 4-methylphenoxide, lithium 2,3-dimethylphenoxide, lithium2,4-dimethylphenoxide, lithium 2,5-dimethylphenoxide, lithium2,6-dimethylphenoxide, lithium 3,4-dimethylphenoxide, lithium2,3,4-trimethylphenoxide, lithium 2,3,5-trimethylphenoxide, lithium2,3,6-trimethylphenoxide, lithium 3,4,5-trimethylphenoxide, lithium2,4,6-trimethylphenoxide, lithium 2,3,4,5-tetramethylphenoxide, lithium2,3,4,6-tetramethylphenoxide, lithium 2,3,5,6-tetramethylphenoxide,lithium pentamethylphenoxide, lithium ethylphenoxide, lithiumn-propylphenoxide, lithium isopropylphenoxide, lithium n-butylphenoxide,lithium sec-butylphenoxide, lithium tert-butylphenoxide, lithiumn-pentylphenoxide, lithium neopentylphenoxide, lithium n-hexylphenoxide,lithium n-octylphenoxide, lithium n-decylphenoxide, lithiumn-dodecylphenoxide, lithium n-tetradecylphenoxide, lithiumnaphthyloxide, and lithium anthracenyloxide; compounds in which lithiumis replaced with sodium or potassium in these compounds; alkali metalhaloaryloxides in which these compounds are substituted with a halogensuch as fluorine, chlorine or bromine atom; alkali metalalkoxyaryloxide, obtained by arbitrarily changing a halogen atom in thehaloaralkyl group into a methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec-butoxy or tert-butoxy group; alkali metal cyanoaryloxides;and alkali metal nitroaryloxides. Preferable examples thereof includelithium phenoxide, lithium 4-methylphenoxide, lithium2,4,6-trimethylphenoxide, sodium phenoxide, sodium 4-methylphenoxide andsodium 2,4,6-trimethylphenoxide.

A commercially available product or the like can be used as the alkalimetal compound (10). Alternatively, the alkali metal compound (10) canalso be produced in the system, for use, through the reaction between analcohol compound and an alkali metal compound.

Examples of such an alkali metal compound used in the production of thealkali metal compound (10) in the system include: alkyllithiums such asmethyllithium, ethyllithium, n-propyllithium, isopropyllithium,n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium,neopentyllithium, amyllithium, n-hexyllithium, n-octyllithium,n-decyllithium, n-dodecyllithium, n-pentadecyllithium andn-eicosyllithium;

aralkyllithiums such as benzyllithium, (2-methylphenyl)methyllithium,(3-methylphenyl)methyllithium, (4-methylphenyl)methyllithium,(2,3-dimethylphenyl)methyllithium, (2,4-dimethylphenyl)methyllithium,(2,5-dimethylphenyl)methyllithium, (2,6-dimethylphenyl)methyllithium,(3,4-dimethylphenyl)methyllithium, (2,3,4-trimethylphenyl)methyllithium,(2,3,5-trimethylphenyl)methyllithium,(2,3,6-trimethylphenyl)methyllithium,(3,4,5-trimethylphenyl)methyllithium,(2,4,6-trimethylphenyl)methyllithium,(2,3,4,5-tetramethylphenyl)methyllithium,(2,3,4,6-tetramethylphenyl)methyllithium,(2,3,5,6-tetramethylphenyl)methyllithium,(pentamethylphenyl)methyllithium, (ethylphenyl)methyllithium,(n-propylphenyl)methyllithium, (isopropylphenyl)methyllithium,(n-butylphenyl)methyllithium, (sec-butylphenyl)methyllithium,(tert-butylphenyl)methyllithium, (n-pentylphenyl)methyllithium,(neopentylphenyl)methyllithium, (n-hexylphenyl)methyllithium,(n-octylphenyl)methyllithium, (n-decylphenyl)methyllithium,(n-dodecylphenyl)methyllithium, (n-tetradecylphenyl)methyllithium,naphthylmethyllithium and anthracenylmethyllithium; and

aryllithiums such as phenyllithium, 2-tolyllithium, 3-tolyllithium,4-tolyllithium, 2,3-xylyllithium, 2,4-xylyllithium, 2,5-xylyllithium,2,6-xylyllithium, 3,4-xylyllithium, 3,5-xylyllithium,2,3,4-trimethylphenyllithium, 2,3,5-trimethylphenyllithium,2,3,6-trimethylphenyllithium, 2,4,6-trimethylphenyllithium,3,4,5-trimethylphenyllithium, 2,3,4,5-tetramethylphenyllithium,2,3,4,6-tetramethylphenyllithium, 2,3,5,6-tetramethylphenyllithium,pentamethylphenyllithium, ethylphenyllithium, n-propylphenyllithium,isopropylphenyllithium, n-butylphenyllithium, sec-butylphenyllithium,tert-butylphenyllithium, n-pentylphenyllithium, neopentylphenyllithium,n-hexylphenyllithium, n-octylphenyllithium, n-decylphenyllithium,n-dodecylphenyllithium, n-tetradecylphenyllithium, naphthyllithium andanthracenyllithium. Methyllithium, benzyllithium and phenyllithium arepreferable.

Moreover, examples of the alcohol compound used include monools such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethylether, ethylene glycol monoethyl ether, phenol, benzyl alcohol,1-phenylethanol, and so on.

Examples of the alkaline earth metal compound represented by the generalformula (11) include: alkaline earth metal alkoxides derived frommonools, such as magnesium dimethoxide, magnesium diethoxide, magnesiumdi-n-propoxide, magnesium diisopropoxide, magnesium di-n-butoxide,magnesium di-sec-butoxide, magnesium di-tert-butoxide, magnesiumdi-n-pentoxide, magnesium dineopentoxide, magnesium dimethoxyethoxide,magnesium diethoxyethoxide, magnesium dibenzyloxide, and magnesiumdi-1-phenylethoxide, and those obtained by changing magnesium in thesecompounds to calcium, strontium or barium; and alkaline earth metalalkoxides derived from diols, such as magnesium ethylenedioxide,magnesium methylethylenedioxide, magnesium 1,2-dimethylethylenedioxide,magnesium tetramethylethylenedioxide, magnesium phenylethylenedioxide,magnesium 1,2-diphenylethylenedioxide, magnesiumtetraphenylethylenedioxide, magnesium cyclopentane-1,2-dioxide,magnesium cyclohexane-1,2-dioxide, magnesium propylene-1,3-dioxide,magnesium 1,3-dimethylpropylene-1,3-dioxide, and magnesium1,3-diphenylpropylene-1,3-dioxide, and those obtained by arbitrarilychanging magnesium in these compounds into calcium, strontium or barium.These compounds encompass all stereoisomers and optical isomers thereof.

A commercially available product or the like can be used as the alkalineearth metal compound (II). Alternatively, the alkaline earth metalcompound (II) can also be produced in the system, for use, through thereaction between an alcohol compound and an alkaline earth metalcompound.

Examples of such an alkaline earth metal compound used in the productionof the alkaline earth alkoxides in the system include Grignard reagentssuch as methylmagnesium chloride, phenylmagnesium chloride,benzylmagnesium chloride, methylmagnesium bromide, phenylmagnesiumbromide and benzylmagnesium bromide. Preferable examples thereof includemethylmagnesium chloride and methylmagnesium bromide. Moreover, examplesof the alcohol compound used include: monools such as methanol, ethanol,n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol,n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, phenol, benzyl alcohol and1-phenylethanol; and diols such as ethylene glycol, propylene glycol,2,3-butanediol, tetramethylethylene glycol, phenylethylene glycol,hydrobenzoin, tetraphenylethylene glycol, cyclopentane-1,2-diol,cyclohexane-1,2-diol, 1,3-propanediol, 2,4-pentanediol,1,3-diphenyl-1,3-propanediol and tartaric acid. These compoundsencompass all stereoisomers and optical isomers thereof.

Examples of the alcohol compound used in the method B include monoolssuch as methanol, ethanol, n-propanol, isopropanol, n-butanol,sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzylalcohol and 1-phenylethanol.

Examples of the base include: inorganic bases such as alkali metalhydroxides and alkali metal carbonates; and organic bases such as aminecompounds, and preferably include amine compounds. Examples of the aminecompounds include, but not particularly limited to: primary amines suchas aniline, chloroaniline, bromoaniline, fluoroaniline, toluidine,anisidine, naphthylamine, benzylamine, propylamine, butylamine andpentylamine; secondary amines such as N-methylaniline, N-ethylaniline,diphenylamine, N-methylchloroaniline, N-methylbromoaniline,N-methylfluoroaniline, pyrrolidine, morpholine and piperidine; tertiaryamines such as trimethylamine, triethylamine, diisopropylethylamine,N,N-dimethylaniline, N,N-dimethylchloroaniline,N,N-dimethylbromoaniline, N,N-dimethylfluoroaniline,N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine,1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene and1,8-diazabicyclo[5,4,0]undec-7-ene; and pyridines such as pyridine,N,N-dimethylaminopyridine, picoline and pipecoline.

The reaction process is not particularly limited, and the reaction ispreferably performed by reacting the transition metal complex (1-1) withthe alkali metal compound (10) (process A-1) or the alkaline earth metalcompound (II) (process A-2) or with the alcohol compound in the presenceof a base (process B), in the presence of a solvent in an inertatmosphere of nitrogen, argon, or the like.

In process A-1, the amount of the alkali metal compound (10) used withrespect to the transition metal complex (1-1) is usually approximately0.5- to 15-fold by mol, preferably approximately 0.8- to 3-fold by mol.

In the method A-2, the amount of the alkaline earth metal compound (II)used with respect to the transition metal complex (1-1) is usuallyapproximately 0.3- to 10-fold by mol, preferably approximately 0.5- to2-fold by mol.

In the method B, the amount of the alcohol compound used with respect tothe transition metal complex (1-1) is usually approximately 0.5- to10-fold by mol, preferably approximately 0.8- to 3-fold by mol, and theamount of the base used with respect to the transition metal complex(1-1) is usually approximately 0.5- to 5-fold by mol, preferablyapproximately 0.8- to 3-fold by mol.

Examples of the solvent that can be used in the reactions include, butnot particularly limited to: aliphatic hydrocarbyl solvents such aspentane, hexane, heptane, octane and decane; aromatic hydrocarbylsolvents such as benzene, toluene, xylene and mesitylene; halogenatedaliphatic hydrocarbyl solvents such as dichloromethane, chloroform anddichloroethane; halogenated aromatic hydrocarbyl solvents such asmonochlorobenzene and dichlorobenzene; ethers such as diethyl ether,dibutyl ether, methyl t-butyl ether and tetrahydrofuran; alcoholscorrespond to the alkali metal compound (10); and mixtures thereof. Theamount thereof used is usually 1- to 200-fold by weight, preferablyapproximately 3- to 30-fold by weight, with respect to the transitionmetal complex (1-1) in each of the processes A-1, A-2 and B.

The reaction temperature is usually −100° C. to the boiling point of thesolvent, preferably approximately −80 to 30° C.

After the reaction, for example, insoluble solid is removed, and thesolvent can be distilled off to obtain the transition metal complex(1-3). The transition metal complex (1-3) can be purified, if necessary,by a usual method such as recrystallization and sublimation.

<Substituted Cyclopentadienes (6-1) to (6-6)>

In the substituted cyclopentadiene compound (6-1), the substituents R²⁸,R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as definedabove.

Examples of the substituted cyclopentadiene compound (6-1) can includethe following compounds:

1-(ethylmethylphenylsilyl)-2-methylcyclopentadiene,1-(ethylmethylphenylsilyl)-3-methylcyclopentadiene,1-(ethylmethylphenylsilyl)-2,3-dimethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2,4-dimethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2,5-dimethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-ethylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-n-propylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-isopropylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-n-butylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-tert-butylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-phenylcyclopentadiene,1-(ethylmethylphenylsilyl)-2-benzylcyclopentadiene,

1-(diethylphenylsilyl)-2-methylcyclopentadiene,1-(diethylphenylsilyl)-3-methylcyclopentadiene,1-(diethylphenylsilyl)-2,3-dimethylcyclopentadiene,1-(diethylphenylsilyl)-2,4-dimethylcyclopentadiene,1-(diethylphenylsilyl)-2,5-dimethylcyclopentadiene,1-(diethylphenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(diethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(diethylphenylsilyl)-2-ethylcyclopentadiene,1-(diethylphenylsilyl)-2-n-propylcyclopentadiene,1-(diethylphenylsilyl)-2-isopropylcyclopentadiene,1-(diethylphenylsilyl)-2-n-butylcyclopentadiene,1-(diethylphenylsilyl)-2-tert-butylcyclopentadiene,1-(diethylphenylsilyl)-2-phenylcyclopentadiene,1-(diethylphenylsilyl)-2-benzylcyclopentadiene,

1-(n-butylmethylphenylsilyl)-2-methylcyclopentadiene,1-(n-butylmethylphenylsilyl)-3-methylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2,3-dimethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2,4-dimethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2,5-dimethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-ethylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-n-propylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-isopropylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-n-butylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-tert-butylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-phenylcyclopentadiene,1-(n-butylmethylphenylsilyl)-2-benzylcyclopentadiene,

1-(cyclohexylmethylphenylsilyl)-2-methylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-3-methylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2,3-dimethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2,4-dimethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2,5-dimethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-ethylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-n-propylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-isopropylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-n-butylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-tert-butylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-phenylcyclopentadiene,1-(cyclohexylmethylphenylsilyl)-2-benzylcyclopentadiene,

1-(methyl(n-octadecyl)phenylsilyl)-2-methylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-3-methylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2,3-dimethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2,4-dimethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2,5-dimethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-ethylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-n-propylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-isopropylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-n-butylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-tert-butylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-phenylcyclopentadiene,1-(methyl(n-octadecyl)phenylsilyl)-2-benzylcyclopentadiene,

1-(benzyldiphenylsilyl)-2-methylcyclopentadiene,1-(benzyldiphenylsilyl)-3-methylcyclopentadiene,1-(benzyldiphenylsilyl)-2,3-dimethylcyclopentadiene,1-(benzyldiphenylsilyl)-2,4-dimethylcyclopentadiene,1-(benzyldiphenylsilyl)-2,5-dimethylcyclopentadiene,1-(benzyldiphenylsilyl)-2,3,5-trimethylcyclopentadiene,1-(benzyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene,1-(benzyldiphenylsilyl)-2-ethylcyclopentadiene,1-(benzyldiphenylsilyl)-2-n-propylcyclopentadiene,1-(benzyldiphenylsilyl)-2-isopropylcyclopentadiene,1-(benzyldiphenylsilyl)-2-n-butylcyclopentadiene,1-(benzyldiphenylsilyl)-2-tert-butylcyclopentadiene,1-(benzyldiphenylsilyl)-2-phenylcyclopentadiene and1-(benzyldiphenylsilyl)-2-benzylcyclopentadiene.

The substituted cyclopentadiene compounds exemplified above may haveisomers differing in the double bond position of the cyclopentadienering. A mixture of these isomers may also be used in the presentinvention.

In the substituted cyclopentadiene compound (6-2), the substituents R³⁹,R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸ and R⁴⁹ are as definedabove.

Examples of the substituted cyclopentadiene compound (6-2) can includethe following compounds:

1-triphenylsilyl-2-methylcyclopentadiene,1-triphenylsilyl-3-methylcyclopentadiene,1-triphenylsilyl-2,3-dimethylcyclopentadiene,1-triphenylsilyl-2,4-dimethylcyclopentadiene,1-triphenylsilyl-2,5-dimethylcyclopentadiene,1-triphenylsilyl-2,3,5-trimethylcyclopentadiene,1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-triphenylsilyl-2-ethylcyclopentadiene,1-triphenylsilyl-2-n-propylcyclopentadiene,1-triphenylsilyl-2-isopropylcyclopentadiene,1-triphenylsilyl-2-n-butylcyclopentadiene,1-triphenylsilyl-2-tert-butylcyclopentadiene,1-triphenylsilyl-2-phenylcyclopentadiene,1-triphenylsilyl-2-benzylcyclopentadiene,

1-(3-methylphenyl)diphenylsilyl-2-methylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-3-methylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2,3-dimethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2,4-dimethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2,5-dimethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2,3,5-trimethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-ethylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-n-propylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-isopropylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-n-butylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-tert-butylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-phenylcyclopentadiene,1-(3-methylphenyl)diphenylsilyl-2-benzylcyclopentadiene,

1-(4-methylphenyl)diphenylsilyl-2-methylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-3-methylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2,3-dimethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2,4-dimethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2,5-dimethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2,3,5-trimethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-ethylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-n-propylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-isopropylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-n-butylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-tert-butylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-phenylcyclopentadiene,1-(4-methylphenyl)diphenylsilyl-2-benzylcyclopentadiene,

1-(3,5-dimethylphenyl)diphenylsilyl-2-methylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-3-methylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2,3-dimethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2,4-dimethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2,5-dimethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2,3,5-trimethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-ethylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-n-propylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-isopropylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-n-butylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-tert-butylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-phenylcyclopentadiene,1-(3,5-dimethylphenyl)diphenylsilyl-2-benzylcyclopentadiene,

1-bis(3,5-dimethylphenyl)phenylsilyl-2-methylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-3-methylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2,3-dimethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2,4-dimethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2,5-dimethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2,3,5-trimethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-ethylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-n-propylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-isopropylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-n-butylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-tert-butylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-phenylcyclopentadiene,1-bis(3,5-dimethylphenyl)phenylsilyl-2-benzylcyclopentadiene,

1-tris(3,5-dimethylphenyl)silyl-2-methylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-3-methylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-ethylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-phenylcyclopentadiene,1-tris(3,5-dimethylphenyl)silyl-2-benzylcyclopentadiene,

1-(4-n-butylphenyl)diphenylsilyl-2-methylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-3-methylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2,3-dimethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2,4-dimethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2,5-dimethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2,3,5-trimethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-ethylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-n-propylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-isopropylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-n-butylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-tert-butylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-phenylcyclopentadiene,1-(4-n-butylphenyl)diphenylsilyl-2-benzylcyclopentadiene,

1-di(4-n-butylphenyl)phenylsilyl-2-methylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-3-methylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2,3-dimethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2,4-dimethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2,5-dimethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2,3,5-trimethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-ethylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-n-propylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-isopropylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-n-butylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-tert-butylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-phenylcyclopentadiene,1-di(4-n-butylphenyl)phenylsilyl-2-benzylcyclopentadiene,

1-tri(4-n-butylphenyl)silyl-2-methylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-3-methylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2,3-dimethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2,4-dimethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2,5-dimethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-ethylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-n-propylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-isopropylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-n-butylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-tert-butylcyclopentadiene,1-tri(4-n-butylphenyl)silyl-2-phenylcyclopentadiene and1-tri(4-n-butylphenyl)silyl-2-benzylcyclopentadiene.

The substituted cyclopentadiene compounds exemplified above may haveisomers differing in the double bond position of the cyclopentadienering. A mixture of these isomers may also be used in the presentinvention.

In the substituted cyclopentadiene compound (6-3), the substituents R⁵⁰,R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹ and R⁶⁰ are as definedabove.

Examples of the substituted cyclopentadiene compound (6-3) can includethe following compounds:

1-dimethylphenylsilyl-tetrahydroindene,1-dimethylphenylsilyl-2-methyltetrahydroindene,1-dimethylphenylsilyl-3-methyltetrahydroindene,9-dimethylphenylsilyl-octahydrofluorene,

1-ethylmethylphenylsilyl-tetrahydroindene,1-ethylmethylphenylsilyl-2-methyltetrahydroindene,1-ethylmethylphenylsilyl-3-methyltetrahydroindene,9-ethylmethylphenylsilyl-octahydrofluorene,1-diethylphenylsilyl-tetrahydroindene,1-diethylphenylsilyl-2-methyltetrahydroindene,1-diethylphenylsilyl-3-methyltetrahydroindene,9-diethylphenylsilyl-octahydrofluorene,1-n-butylmethylphenylsilyl-tetrahydroindene,1-n-butylmethylphenylsilyl-2-methyltetrahydroindene,1-n-butylmethylphenylsilyl-3-methyltetrahydroindene,9-n-butylmethylphenylsilyl-octahydrofluorene,1-cyclohexylmethylphenylsilyl-tetrahydroindene,1-cyclohexylmethylphenylsilyl-2-methyltetrahydroindene,1-cyclohexylmethylphenylsilyl-3-methyltetrahydroindene,9-cyclohexylmethylphenylsilyl-octahydrofluorene,

1-methyldiphenylsilyl-tetrahydroindene,1-methyldiphenylsilyl-2-methyltetrahydroindene,1-methyldiphenylsilyl-3-methyltetrahydroindene,9-methyldiphenylsilyl-octahydrofluorene,

1-triphenylsilyl-tetrahydroindene,1-triphenylsilyl-2-methyltetrahydroindene,1-triphenylsilyl-3-methyltetrahydroindene and9-triphenylsilyl-octahydrofluorene.

The substituted cyclopentadiene compounds exemplified above may haveisomers differing in the double bond position of the cyclopentadienering. A mixture of these isomers may also be used in the presentinvention.

In the substituted cyclopentadiene compound (6-4), the substituents R⁶¹,R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰ and R⁷¹ are as definedabove.

Examples of the substituted cyclopentadiene compound (6-4) can includethe following compounds:

1-dimethyl(4-methylphenyl)silyl-2-methylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-3-methylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2,3-dimethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2,4-dimethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2,5-dimethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-ethylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-n-propylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-isopropylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-n-butylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-tert-butylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-phenylcyclopentadiene,1-dimethyl(4-methylphenyl)silyl-2-benzylcyclopentadiene,

1-dimethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-3-methylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-ethylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-phenylcyclopentadiene,1-dimethyl(3,5-dimethylphenyl)silyl-2-benzylcyclopentadiene,

1-dimethyl(2,4,6-trimethylphenyl)silyl-2-methylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-3-methylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3-dimethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2,4-dimethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2,5-dimethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-ethylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-n-propylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-isopropylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-n-butylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-tert-butylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-phenylcyclopentadiene,1-dimethyl(2,4,6-trimethylphenyl)silyl-2-benzylcyclopentadiene,

1-dimethyl(4-methoxyphenyl)silyl-2-methylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-3-methylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2,3-dimethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2,4-dimethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2,5-dimethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-ethylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-n-propylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-isopropylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-n-butylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-tert-butylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-phenylcyclopentadiene,1-dimethyl(4-methoxyphenyl)silyl-2-benzylcyclopentadiene,

1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-methylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-3-methylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3-dimethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,4-dimethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,5-dimethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,5-trimethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-ethylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-n-propylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-isopropylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-n-butylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-tert-butylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-phenylcyclopentadiene,1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2-benzylcyclopentadiene,

1-(9-anthryl)dimethylsilyl-2-methylcyclopentadiene,1-(9-anthryl)dimethylsilyl-3-methylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2,3-dimethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2,4-dimethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2,5-dimethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2,3,5-trimethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-ethylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-n-propylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-isopropylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-n-butylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-tert-butylcyclopentadiene,1-(9-anthryl)dimethylsilyl-2-phenylcyclopentadiene and1-(9-anthryl)dimethylsilyl-2-benzylcyclopentadiene.

The substituted cyclopentadiene compounds exemplified above may haveisomers differing in the double bond position of the cyclopentadienering. A mixture of these isomers may also be used in the presentinvention.

In the substituted cyclopentadiene compound (6-5), the substituents R⁷²,R⁷³, R⁷⁴, R⁷⁵, R⁷⁶, R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹ and R⁸² are as definedabove.

Examples of the substituted cyclopentadiene compound (6-5) can includethe following compounds:

1-methyl(4-methylphenyl)phenylsilyl-2-methylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-3-methylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2,3-dimethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2,4-dimethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2,5-dimethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2,3,5-trimethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-ethylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-n-propylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-isopropylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-n-butylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-tert-butylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-phenylcyclopentadiene,1-methyl(4-methylphenyl)phenylsilyl-2-benzylcyclopentadiene,

1-(4-n-butylphenyl)methylphenylsilyl-2-methylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-3-methylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2,3-dimethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2,4-dimethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2,5-dimethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2,3,5-trimethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-ethylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-n-propylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-isopropylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-n-butylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-tert-butylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-phenylcyclopentadiene,1-(4-n-butylphenyl)methylphenylsilyl-2-benzylcyclopentadiene,

1-di(4-n-butylphenyl)methylsilyl-2-methylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-3-methylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2,3-dimethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2,4-dimethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2,5-dimethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2,3,5-trimethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-ethylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-n-propylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-isopropylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-n-butylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-tert-butylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-phenylcyclopentadiene,1-di(4-n-butylphenyl)methylsilyl-2-benzylcyclopentadiene,

1-methyl(3,5-dimethylphenyl)phenylsilyl-2-methylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-3-methylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2,3-dimethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2,4-dimethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2,5-dimethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2,3,5-trimethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-ethylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-n-propylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-isopropylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-n-butylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-tert-butylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-phenylcyclopentadiene,1-methyl(3,5-dimethylphenyl)phenylsilyl-2-benzylcyclopentadiene,

1-methylbis(3,5-dimethylphenyl)silyl-2-methylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-3-methylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-ethylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadiene,1-methylbis(3,5-dimethylphenyl)silyl-2-phenylcyclopentadiene and1-methylbis(3,5-dimethylphenyl)silyl-2-benzylcyclopentadiene.

The substituted cyclopentadiene compounds exemplified above may haveisomers differing in the double bond position of the cyclopentadienering. A mixture of these isomers may also be used in the presentinvention.

In the substituted cyclopentadiene compound (6-6), the substituents R⁸³,R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰, R⁹¹, R⁹² and R⁹³ are as definedabove.

Examples of the substituted cyclopentadiene compound (6-6) can includethe following compounds:

1-dimethylphenylsilyl-2-methylcyclopentadiene,1-dimethylphenylsilyl-3-methylcyclopentadiene,1-dimethylphenylsilyl-2,3-dimethylcyclopentadiene,1-dimethylphenylsilyl-2,4-dimethylcyclopentadiene,1-dimethylphenylsilyl-2,5-dimethylcyclopentadiene,1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadiene,1-dimethylphenylsilyl-2-ethylcyclopentadiene,1-dimethylphenylsilyl-2-n-propylcyclopentadiene,1-dimethylphenylsilyl-2-isopropylcyclopentadiene,1-dimethylphenylsilyl-2-n-butylcyclopentadiene,1-dimethylphenylsilyl-2-tert-butylcyclopentadiene,1-dimethylphenylsilyl-2-phenylcyclopentadiene and1-dimethylphenylsilyl-2-benzylcyclopentadiene.

<Process for Producing Substituted Cyclopentadienes (6-1) to (6-6)>

The substituted cyclopentadiene compounds represented by the generalformulas (6-1) to (6-6) can be produced, for example, by the steps of:reacting substituted cyclopentadiene compounds represented by generalformulas (12-1) to (12-6) with a base in the presence of an aminecompound; and

reacting the reaction products of the substituted cyclopentadienecompounds (12-1) to (12-6) and the base with silicon halide compoundsrepresented by general formulas (13-1) to (13-6).

The substituted cyclopentadiene compounds represented by the generalformulas (12-1) to (12-6) are as follows:

wherein R²⁸, R²⁹, R³⁰ and R³¹ are as defined above, andthe moiety

represents

wherein R³⁹, R⁴⁰, R⁴¹ and R⁴² are as defined above, andthe moiety

represents

a substituted cyclopentadiene compound represented by

wherein R⁴⁹, R⁵⁰, R⁵¹ and R⁵² are as defined above, andthe moiety

represents

wherein R⁶¹, R⁶², R⁶³ and R⁶⁴ are as defined above, andthe moiety

represents

wherein R⁷², R⁷³, R⁷⁴ and R⁷⁵ are as defined above, andthe moiety

represents

wherein R⁸³, R⁸⁴, R⁸⁵ and R⁸⁶ are as defined above, andthe moiety

represents

Examples of the substituted cyclopentadiene compounds (12-1), (12-2),(12-4) and (12-5) can include the following compounds:

methylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene,1,3,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene,ethylcyclopentadiene, 1,2-diethylcyclopentadiene,1,3-diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene,1,3,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene,n-propylcyclopentadiene, isopropylcyclopentadiene,n-butylcyclopentadiene, sec-butylcyclopentadiene,tert-butylcyclopentadiene, n-pentylcyclopentadiene,neopentylcyclopentadiene, n-hexylcyclopentadiene,n-octylcyclopentadiene, phenylcyclopentadiene, naphthylcyclopentadiene,trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene andtert-butyldimethylsilylcyclopentadiene.

Examples of the substituted cyclopentadiene compound (12-3) can includethe following compounds:

tetrahydroindene, 2-methyltetrahydroindene, 3-methyltetrahydroindene,2,3-dimethyltetrahydroindene, 2-ethyltetrahydroindene,2-n-propyltetrahydroindene, 2-isopropyltetrahydroindene,2-n-butyltetrahydroindene, 2-sec-butyltetrahydroindene,2-tert-butyltetrahydroindene, 2-n-pentyltetrahydroindene,2-neopentyltetrahydroindene, 2-amyltetrahydroindene,2-n-hexyltetrahydroindene, 2-cyclohexyltetrahydroindene,2-n-octyltetrahydroindene, 2-n-decyltetrahydroindene,2-phenyltetrahydroindene, 2-benzyltetrahydroindene,2-naphthyltetrahydroindene, 2-methoxytetrahydroindene,2-phenoxytetrahydroindene, 2-benzyloxytetrahydroindene,2-dimethylaminotetrahydroindene, 2-trimethylsilyltetrahydroindene andoctahydrofluorene.

Examples of the substituted cyclopentadiene compound (12-6) can includethe following compounds:

methylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene,1,3,4-trimethylcyclopentadiene, ethylcyclopentadiene,1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene,1,2,3-triethylcyclopentadiene, 1,3,4-triethylcyclopentadiene,1,2,3,4-tetraethylcyclopentadiene, n-propylcyclopentadiene,isopropylcyclopentadiene, n-butylcyclopentadiene,sec-butylcyclopentadiene, tert-butylcyclopentadiene,n-pentylcyclopentadiene, neopentylcyclopentadiene,n-hexylcyclopentadiene, n-octylcyclopentadiene, phenylcyclopentadiene,naphthylcyclopentadiene, trimethylsilylcyclopentadiene,triethylsilylcyclopentadiene and tert-butyldimethylsilylcyclopentadiene.

The silicon halide compounds represented by the general formulas (13-1)to (13-6) are as follows:

wherein R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above, andX¹⁷ is a halogen atom;

wherein R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸ and R⁴⁹ are as defined above, andX¹⁸ is a halogen atom;

wherein R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹ and R⁶⁰ are as defined above, andX¹⁹ is a halogen atom;

wherein R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰ and R⁷¹ are as defined above, andX²⁰ is a halogen atom;

wherein R⁷⁶, R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹ and R⁸² are as defined above, andX²¹ is a halogen atom; and

wherein R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰, R⁹¹, R⁹² and R⁹³ are as defined above, andX²² is a halogen atom.

Examples of the silicon halide compound (13-1) can include the followingcompounds:

chloroethylmethylphenylsilane, chlorodiethylphenylsilane,chloromethyl(n-propyl)phenylsilane, chloromethyl(isopropyl)phenylsilane,chloro(n-butyl)methylphenylsilane, chloro(sec-butyl)methylphenylsilane,chloro(tert-butyl)methylphenylsilane,chloromethyl(n-pentyl)phenylsilane, chloromethyl(neopentyl)phenylsilane,amylchloromethylphenylsilane, chloro(n-hexyl)methylphenylsilane,chlorocyclohexylmethylphenylsilane, chloromethyl(n-octyl)phenylsilane,chloro(n-decyl)methylphenylsilane, chloro(n-dodecyl)methylphenylsilane,chloromethyl(n-octadecyl)phenylsilane, chlorobenzyldiphenylsilane,

chloro(n-butyl)methyl(3-methylphenyl)silane,chloro(n-butyl)methyl(4-methylphenyl)silane,chloro(n-butyl)methyl(3,5-dimethylphenyl)silane,chloro(n-butyl)methyl(4-n-butylphenyl)silane,chloro(n-butyl)methyl(4-phenylphenyl)silane,chloro(n-butyl)methyl(4-methoxyphenyl)silane,chloro(n-butyl)methyl(4-phenoxyphenyl)silane,chloro(n-butyl)methyl(4-trimethylsilylphenyl)silane,chloro(n-butyl)methyl(4-dimethylaminophenyl)silane andchloro(n-butyl)methyl(4-benzyloxyphenyl)silane. Moreover, compounds inwhich “chloro” in these compounds exemplified above are replaced with“fluoro”, “bromo” or “iodo” are also included therein.

Examples of the silicon halide compound (13-2) can include the followingcompounds:

chlorotriphenylsilane, chloro(2-methylphenyl)diphenylsilane,chloro(3-methylphenyl)diphenylsilane,chloro(4-methylphenyl)diphenylsilane,chloro(2,3-dimethylphenyl)diphenylsilane,chloro(2,4-dimethylphenyl)diphenylsilane,chloro(2,5-dimethylphenyl)diphenylsilane,chloro(2,6-dimethylphenyl)diphenylsilane,chloro(3,4-dimethylphenyl)diphenylsilane,chloro(3,5-dimethylphenyl)diphenylsilane,chloro(3,6-dimethylphenyl)diphenylsilane,chloro(2,3,4-trimethylphenyl)diphenylsilane,chloro(2,3,5-trimethylphenyl)diphenylsilane,chloro(2,3,6-trimethylphenyl)diphenylsilane,chloro(2,4,5-trimethylphenyl)diphenylsilane,chloro(2,4,6-trimethylphenyl)diphenylsilane,chloro(2,3,4,5-tetramethylphenyl)diphenylsilane,chloro(2,3,4,6-tetramethylphenyl)diphenylsilane,chloro(2,3,4,5,6-pentamethylphenyl)diphenylsilane,chloro(4-ethylphenyl)diphenylsilane,chloro(4-isopropylphenyl)diphenylsilane,chloro(4-n-butylphenyl)diphenylsilane,chloro(4-sec-butylphenyl)diphenylsilane,chloro(4-tert-butylphenyl)diphenylsilane,chloro(4-trimethylsilylphenyl)diphenylsilane,chloro(4-methoxyphenyl)diphenylsilane,chloro(4-dimethylaminophenyl)diphenylsilane,chloro(4-phenoxyphenyl)diphenylsilane,chloro(4-benzyloxyphenyl)diphenylsilane,chlorobis(2,3-dimethylphenyl)phenylsilane,chlorotris(2,3-dimethylphenyl)silane,chlorodi(n-butylphenyl)phenylsilane and chlorotri(n-butylphenyl)silane.Moreover, compounds in which “chloro” in these compounds exemplifiedabove are replaced with “fluoro”, “bromo” or “iodo” are also includedtherein.

Examples of the silicon halide compound (13-3) can include the followingcompounds:

chlorodimethylphenylsilane, chloroethylmethylphenylsilane,chlorodiethylphenylsilane, chloromethyl(n-propyl)phenylsilane,chloromethyl(isopropyl)phenylsilane, chloro(n-butyl)methylphenylsilane,chloro(sec-butyl)methylphenylsilane,chloro(tert-butyl)methylphenylsilane,chloromethyl(n-pentyl)phenylsilane, chloromethyl(neopentyl)phenylsilane,amylchloromethylphenylsilane, chloro(n-hexyl)methylphenylsilane,chlorocyclohexylmethylphenylsilane, chloromethyl(n-octyl)phenylsilane,chloro(n-decyl)methylphenylsilane, chloro(n-dodecyl)methylphenylsilane,chloromethyl(n-octadecyl)phenylsilane, chlorobenzyldiphenylsilane,

chlorodimethyl(3-methylphenyl)silane,chlorodimethyl(4-methylphenyl)silane,chlorodimethyl(3,5-dimethylphenyl)silane,chlorodimethyl(4-n-butylphenyl)silane,chlorodimethyl(4-phenylphenyl)silane,chlorodimethyl(4-methoxyphenyl)silane,chlorodimethyl(4-phenoxyphenyl)silane,chlorodimethyl(4-trimethylsilylphenyl)silane,chlorodimethyl(4-dimethylaminophenyl)silane,chlorodimethyl(4-benzyloxyphenyl)silane,

chloro(n-butyl)methyl(3-methylphenyl)silane,chloro(n-butyl)methyl(4-methylphenyl)silane,chloro(n-butyl)methyl(3,5-dimethylphenyl)silane,chloro(n-butyl)methyl(4-n-butylphenyl)silane,chloro(n-butyl)methyl(4-phenylphenyl)silane,chloro(n-butyl)methyl(4-methoxyphenyl)silane,chloro(n-butyl)methyl(4-phenoxyphenyl)silane,chloro(n-butyl)methyl(4-trimethylsilylphenyl)silane,chloro(n-butyl)methyl(4-dimethylaminophenyl)silane,chloro(n-butyl)methyl(4-benzyloxyphenyl)silane,

chloromethyldiphenylsilane, chloromethyl(2-methylphenyl)phenylsilane,chloromethyl(3-methylphenyl)phenylsilane,chloromethyl(4-methylphenyl)phenylsilane,chloromethyl(2,3-dimethylphenyl)phenylsilane,chloromethyl(2,4-dimethylphenyl)phenylsilane,chloromethyl(2,5-dimethylphenyl)phenylsilane,chloromethyl(2,6-dimethylphenyl)phenylsilane,chloromethyl(3,4-dimethylphenyl)phenylsilane,chloromethyl(3,5-dimethylphenyl)phenylsilane,chloromethyl(3,6-dimethylphenyl)phenylsilane,chloromethyl(2,3,4-trimethylphenyl)phenylsilane,chloromethyl(2,3,5-trimethylphenyl)phenylsilane,chloromethyl(2,3,6-trimethylphenyl)phenylsilane,chloromethyl(2,4,5-trimethylphenyl)phenylsilane,chloromethyl(2,4,6-trimethylphenyl)phenylsilane,chloromethyl(2,3,4,5-tetramethylphenyl)phenylsilane,chloromethyl(2,3,4,6-tetramethylphenyl)phenylsilane,chloromethyl(2,3,4,5,6-pentamethylphenyl)phenylsilane,chloromethyl(4-ethylphenyl)phenylsilane,chloromethyl(4-isopropylphenyl)phenylsilane,chloromethyl(4-n-butylphenyl)phenylsilane,chloromethyl(4-sec-butylphenyl)phenylsilane,chloromethyl(4-tert-butylphenyl)phenylsilane,chloromethyl(4-trimethylsilylphenyl)phenylsilane,chloromethyl(4-methoxyphenyl)phenylsilane,chloromethyl(4-dimethylaminophenyl)phenylsilane,chloromethyl(4-phenoxyphenyl)phenylsilane,chloromethyl(4-benzyloxyphenyl)phenylsilane,chloromethylbis(2,3-dimethylphenyl)silane,chloromethyldi(4-n-butylphenyl)silane,

chlorotriphenylsilane, chloro(2-methylphenyl)diphenylsilane,chloro(3-methylphenyl)diphenylsilane,chloro(4-methylphenyl)diphenylsilane,chloro(2,3-dimethylphenyl)diphenylsilane,chloro(2,4-dimethylphenyl)diphenylsilane,chloro(2,5-dimethylphenyl)diphenylsilane,chloro(2,6-dimethylphenyl)diphenylsilane,chloro(3,4-dimethylphenyl)diphenylsilane,chloro(3,5-dimethylphenyl)diphenylsilane,chloro(3,6-dimethylphenyl)diphenylsilane,chloro(2,3,4-trimethylphenyl)diphenylsilane,chloro(2,3,5-trimethylphenyl)diphenylsilane,chloro(2,3,6-trimethylphenyl)diphenylsilane,chloro(2,4,5-trimethylphenyl)diphenylsilane,chloro(2,4,6-trimethylphenyl)diphenylsilane,chloro(2,3,4,5-tetramethylphenyl)diphenylsilane,chloro(2,3,4,6-tetramethylphenyl)diphenylsilane,chloro(2,3,4,5,6-pentamethylphenyl)diphenylsilane,chloro(4-ethylphenyl)diphenylsilane,chloro(4-isopropylphenyl)diphenylsilane,chloro(4-n-butylphenyl)diphenylsilane,chloro(4-sec-butylphenyl)diphenylsilane,chloro(4-tert-butylphenyl)diphenylsilane,chloro(4-trimethylsilylphenyl)diphenylsilane,chloro(4-methoxyphenyl)diphenylsilane,chloro(4-dimethylaminophenyl)diphenylsilane,chloro(4-phenoxyphenyl)diphenylsilane,chloro(4-benzyloxyphenyl)diphenylsilane,chlorobis(2,3-dimethylphenyl)phenylsilane,chlorotris(2,3-dimethylphenyl)silane,chlorodi(n-butylphenyl)phenylsilane and chlorotri(n-butylphenyl)silane.Moreover, compounds in which “chloro” in these compounds exemplifiedabove are replaced with “fluoro”, “bromo” or “iodo” are also includedtherein.

Examples of the silicon halide compound (13-4) can include the followingcompounds:

chlorodimethyl(2-methylphenyl)silane,chlorodimethyl(3-methylphenyl)silane,chlorodimethyl(4-methylphenyl)silane,chlorodimethyl(2,3-dimethylphenyl)silane,chlorodimethyl(2,4-dimethylphenyl)silane,chlorodimethyl(2,5-dimethylphenyl)silane,chlorodimethyl(2,6-dimethylphenyl)silane,chlorodimethyl(3,4-dimethylphenyl)silane,chlorodimethyl(3,5-dimethylphenyl)silane,chlorodimethyl(3,6-dimethylphenyl)silane,chlorodimethyl(2,3,4-trimethylphenyl)silane,chlorodimethyl(2,3,5-trimethylphenyl)silane,chlorodimethyl(2,3,6-trimethylphenyl)silane,chlorodimethyl(2,3,4,5-tetramethylphenyl)silane,chlorodimethyl(2,3,4,6-tetramethylphenyl)silane,chlorodimethyl(2,3,4,5,6-pentamethylphenyl)silane,chlorodimethyl(4-n-butylphenyl)silane,chlorodimethyl(4-tert-butylphenyl)silane,chlorodimethyl(3,5-di-tert-butylphenyl)silane,chlorodimethyl(3-tert-butyl-5-methylphenyl)silane,chlorodimethyl(3,5-tert-butyl-4-methylphenyl)silane,(9-anthryl)chlorodimethylsilane,chloro(3,5-bis(trifluoromethyl)phenyl)dimethylsilane,chlorodimethyl(4-chlorophenyl)silane,chlorodimethyl(3,5-dichlorophenyl)silane,chlorodimethyl(4-fluorophenyl)silane andchlorodimethyl(4-bromophenyl)silane. Moreover, compounds in which“chloro” in these compounds exemplified above are replaced with“fluoro”, “bromo” or “iodo” are also included therein.

Examples of the silicon halide compound (13-5) can include the followingcompounds:

chloromethyl(2-methylphenyl)phenylsilane,chloromethyl(3-methylphenyl)phenylsilane,chloromethyl(4-methylphenyl)phenylsilane,chloromethyl(2,3-dimethylphenyl)phenylsilane,chloromethyl(2,4-dimethylphenyl)phenylsilane,chloromethyl(2,5-dimethylphenyl)phenylsilane,chloromethyl(2,6-dimethylphenyl)phenylsilane,chloromethyl(3,4-dimethylphenyl)phenylsilane,chloromethyl(3,5-dimethylphenyl)phenylsilane,chloromethyl(3,6-dimethylphenyl)phenylsilane,chloromethyl(2,3,4-trimethylphenyl)phenylsilane,chloromethyl(2,3,5-trimethylphenyl)phenylsilane,chloromethyl(2,3,6-trimethylphenyl)phenylsilane,chloromethyl(2,4,5-trimethylphenyl)phenylsilane,chloromethyl(2,4,6-trimethylphenyl)phenylsilane,chloromethyl(2,3,4,5-tetramethylphenyl)phenylsilane,chloromethyl(2,3,4,6-tetramethylphenyl)phenylsilane,chloromethyl(2,3,4,5,6-pentamethylphenyl)phenylsilane,chloromethyl(4-ethylphenyl)phenylsilane,chloromethyl(4-isopropylphenyl)phenylsilane,chloromethyl(4-n-butylphenyl)phenylsilane,chloromethyl(4-sec-butylphenyl)phenylsilane,chloromethyl(4-tert-butylphenyl)phenylsilane,chloromethyl(4-trimethylsilylphenyl)(4-methylphenyl)silane,chloromethyl(4-methoxyphenyl)(4-methylphenyl)silane,chloromethyl(4-dimethylaminophenyl)(4-methylphenyl)silane,chloromethyl(4-phenoxyphenyl)(4-methylphenyl)silane,chloromethyl(4-benzyloxyphenyl)(4-methylphenyl)silane,chloromethyl(4-methylphenyl)(2,3-dimethylphenyl)silane andchloromethyl(4-n-butylphenyl)(4-methylphenyl)silane. Moreover, compoundsin which “chloro” in these compounds exemplified above are replaced with“fluoro”, “bromo” or “iodo” are also included therein.

Examples of the silicon halide compound (13-6) can include the followingcompounds:

chlorodimethylphenylsilane, bromodimethylphenylsilane,fluorodimethylphenylsilane and iododimethylphenylsilane.

Examples of the base to be reacted with the substituted cyclopentadienecompounds (12-1) to (12-6) include: alkali metal hydrides such aslithium hydride, sodium hydride and potassium hydride; alkaline earthmetal hydrides such as calcium hydride; and organic alkali metalcompounds typified by organic lithium compounds such as methyllithium,ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium,lithiumtrimethylsilyl acetylide, lithium acetylide,trimethylsilylmethyllithium, vinyllithium, phenyllithium andallyllithium. The amount thereof used is usually in the range of 0.5- to3-fold by mol, preferably in the range of 0.9- to 2-fold by mol, withrespect to the substituted cyclopentadiene compound. A usualcommercially available mineral oil-containing product can be useddirectly as sodium hydride or potassium hydride. Of course, prior to theusage, the mineral oil may be removed, by washing with a hydrocarbylsolvent such as hexane.

Examples of the amine compound include: Primary amines including primaryanilines such as aniline, chloroaniline, bromoaniline, fluoroaniline,dichloroaniline, dibromoaniline, difluoroaniline, trichloroaniline,tribromoaniline, trifluoroaniline, tetrachloroaniline,tetrabromoaniline, tetrafluoroaniline, pentachloroaniline,pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline,phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline,ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline,isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline,t-butoxyaniline, phenoxyaniline, methylaniline, ethylaniline,n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline,isobutylaniline, t-butylaniline, dimethylaniline, diethylaniline,di-n-propylaniline, diisopropylaniline, di-n-butylaniline,di-sec-butylaniline, diisobutylaniline, di-t-butylaniline,trimethylaniline, triethylaniline, diisopropylaniline, phenylaniline,benzylaniline, aminobenzoic acid, methyl aminobenzoate, ethylaminobenzoate, n-propyl aminobenzoate, isopropyl aminobenzoate, n-butylaminobenzoate, isobutyl aminobenzoate, sec-butyl aminobenzoate andt-butyl aminobenzoate, and further including other primary aminesincluding naphthylamine, naphthylmethylamine, benzylamine, propylamine,butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine,octylamine, 2-aminopyridine, 3-aminopyridine and 4-aminopyridine;

secondary amines such as N-methylaniline, N-ethylaniline, diphenylamine,N-methylchloroaniline, N-methylbromoaniline, N-methylfluoroaniline,N-methylanisidine, N-methylmethylaniline, N-methylethylaniline,N-methyl-n-propylaniline, N-methylisopropylaniline, diethylamine,dipropylamine, diisopropylamine, dipentylamine, dihexylamine,dicyclohexylamine, diheptylamine, dioctylamine, morpholine, piperidine,2,2,6,6-tetramethylpiperidine, pyrrolidine, 2-methylaminopyridine,3-methylaminopyridine and 4-methylaminopyridine; and

tertiary amines such as N,N-dimethylaniline, N,N-dimethylchloroaniline,N,N-dimethylbromoaniline, N,N-dimethylfluoroaniline,N,N-dimethylanisidine, N-methylmethylaniline, N,N-dimethylethylaniline,N,N-dimethyl-n-propylaniline, N,N-dimethylisopropylaniline,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene,1,8-diazabicyclo[5.4.0]undec-7-ene, 2-dimethylaminopyridine,3-dimethylaminopyridine, 4-dimethylaminopyridine, trimethylamine,triethylamine, tri-n-propylamine, tri-n-butylamine,diisopropylethylamine, tri-n-octylamine, tri-n-decylamine andtriphenylamine. Preferably primary or secondary amines, more preferablyprimary amines are used.

The amount thereof used is usually in the range of 0.001- to 2-fold bymol, preferably in the range of 0.01- to 0.5-fold by mol, with respectto the metal hydride. The reaction is usually performed in a solventinert to the reaction. Examples of such a solvent include aproticsolvents such as: aromatic hydrocarbyl solvents such as benzene, tolueneand xylene; aliphatic hydrocarbyl solvents such as pentane, hexane,heptane, octane and cyclohexane; ether solvents such as diethyl ether,methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solventssuch as hexamethylphosphoric amide, dimethylformamide, dimethylacetamideand N-methylpyrrolidone; and halogen solvents such as chlorobenzene anddichlorobenzene. These solvents are used alone or as a mixture of two ormore thereof, and the amount thereof used is usually in the range of 1-to 200-fold by weight, preferably in the range of 3- to 30-fold byweight, with respect to the cyclopentadiene.

For the reaction, for example, any of the substituted cyclopentadienecompounds (12-1) to (12-6), the base and the amine compound may be mixedsimultaneously in a solvent, or the base and the amine compound aremixed in advance and then any of the substituted cyclopentadienecompounds (12-1) to (12-6) may be added to the mixture. The reactiontemperature is not particularly limited, and a temperature region thateliminates the need of low temperature equipment is industriallypreferable and is, for example, in the range of 0 to 70° C., preferablyin the range of 10 to 60° C. This reaction efficiently produces a metalsalt of any of the substituted cyclopentadiene compounds (12-1) to(12-6). The metal salt of any of the substituted cyclopentadienecompounds (12-1) to (12-6) thus obtained may be used directly in theform of the reaction mixture or may be taken from the reaction mixture.The former case usually suffices.

The reaction for obtaining any of the substituted cyclopentadienecompounds (6-1) to (6-6) is usually performed in a solvent inert to thereaction. Examples of such a solvent include aprotic solvents such as:aromatic hydrocarbyl solvents such as benzene, toluene and xylene;aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octaneand cyclohexane; ether solvents such as diethyl ether, methyl t-butylether, tetrahydrofuran and 1,4-dioxane; amide solvents such ashexamethylphosphoric amide, dimethylformamide, dimethylacetamide andN-methylpyrrolidone; and halogen solvents such as chlorobenzene anddichlorobenzene. These solvents are used alone or as a mixture of two ormore thereof, and the amount thereof used is usually in the range of 1-to 200-fold by weight, preferably in the range of 3- to 30-fold byweight, with respect to any of the substituted cyclopentadiene compounds(12-1) to (12-6). This reaction is usually performed, for example, bymixing the base, the amine compound and any of the substitutedcyclopentadiene compounds (12-1) to (12-6) in a solvent and then addingany of the silicon halide compounds (13-1) to (13-6) to the mixture.However, even when a method in which these components are mixedsimultaneously is employed, the substituted cyclopentadiene compounds(12-1) to (12-6) of interest can be produced. The reaction temperatureis not particularly limited, and a temperature region that eliminatesthe need of low temperature equipment is industrially advantageous andis, for example, in the range of 0 to 70° C., preferably in the range of10 to 60° C.

The amount of the substituted cyclopentadienes (12-1) to (12-6) used isusually in the range of 0.5- to 5-fold by mol, preferably in the rangeof 0.8- to 3-fold by mol, with respect to the silicon halide compounds(13-1) to (13-6).

After the completion of the reaction, water, an aqueous sodiumbicarbonate solution, an aqueous sodium carbonate solution, an aqueousammonium chloride solution or an aqueous solution of hydrochloric acidor the like is added to the obtained reaction mixture. Then, organic andaqueous layers are separated to obtain solutions of any of thesubstituted cyclopentadiene compounds (12-1) to (12-6) as the organiclayer. When water-compatible solvent is used in the reaction or when theamount of the solvent used in the reaction is too small to easilyseparate organic and aqueous layers, a water-insoluble organic solventsuch as toluene, ethyl acetate or chlorobenzene may be added to thereaction mixture as needed, followed by separation into organic andaqueous layers. The obtained organic layer is concentrated to obtain anyof the substituted cyclopentadiene compounds (12-1) to (12-6). Theobtained substituted cyclopentadiene compound may be purified, ifnecessary, by a method such as distillation or column chromatographytreatment.

<Activating Co-Catalytic Component>

Examples of the activating co-catalytic component can include compounds(A) and (B) shown below. These compounds (A) and (B) may be used incombination.

Compound (A): one or more aluminum compounds selected from the compoundgroup consisting of the following compounds (A1) to (A3):

(A1): an organic aluminum compound represented by a general formula(E¹)_(a)Al(G)_(3-a),

(A2): a cyclic aluminoxane having a structure represented by a generalformula {—Al(E²)-O-}_(b), and

(A3): a linear aluminoxane having a structure represented by a generalformula E³{—Al(E³)-O—}_(c)Al(E³)₂, wherein

E¹, E² and E³ each represent a hydrocarbyl group having 1 to 8 carbonatoms; G represents a hydrogen atom or a halogen atom; a represents aninteger of 1 to 3; b represents an integer of 2 or more; c represents aninteger of 1 or more; in the case that more than one E¹ groups exist,the E¹ groups may be the same or different from each other; in the casethat more than one G groups exist, the G groups may be the same ordifferent from each other; the E² groups may be the same or differentfrom each other; and the E³ groups may be the same or different fromeach other; and Compound (B): one or more boron compounds selected fromthe compound group consisting of the following compounds (B1) to (B3):

(B1): a boron compound represented by a general formula BQ¹Q²Q³

(B2): a borate compound represented by a general formula T⁺(BQ¹Q²Q³Q⁴)⁻,and

(B3): a borate compound represented by a general formula(L-H)⁺(BQ¹Q²Q³Q⁴)⁻, wherein

B represents a trivalent boron atom; Q¹, Q², Q³ and Q⁴ are the same asor different from each other and each represent a halogen atom, ahydrocarbyl group having 1 to 20 carbon atoms which may be substitutedwith a halogen atom, a hydrocarbylsilyl group having 1 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms or adihydrocarbylamino group having 2 to 20 carbon atoms; T⁺ represents aninorganic or organic cation; and (L-H)⁺ represents a Broensted acid.

In the compounds (A1) to (A3), examples of the hydrocarbyl group having1 to 8 carbon atoms in E¹, E² and E³ include alkyl having 1 to 8 carbonatoms. Examples of the alkyl groups having 1 to 8 carbon atoms includemethyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normalpentyl and neopentyl groups.

Examples of the organic aluminum compound (A1) represented by thegeneral formula (E¹)_(a)Al(G)_(3-a) include trialkylaluminums,dialkylaluminum chlorides, alkylaluminum dichlorides and dialkylaluminumhydrides. Examples of the trialkylaluminum include trimethylaluminum,triethylaluminum, tripropylaluminum, triisobutylaluminum andtrihexylaluminum. Examples of the dialkylaluminum chloride includedimethylaluminum chloride, diethylaluminum chloride, dipropylaluminumchloride, diisobutylaluminum chloride and dihexylaluminum chloride.Examples of the alkylaluminum dichloride include methylaluminumdichloride, ethylaluminum dichloride, propylaluminum dichloride,isobutylaluminum dichloride and hexylaluminum dichloride. Examples ofthe dialkylaluminum hydride include dimethylaluminum hydride,diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride and dihexylaluminum hydride.

Examples of E² and E³ in (A2): cyclic aluminoxane having a structurerepresented by the general formula {—Al(E²)-O—}_(b) and (A3): linearaluminoxane having a structure represented by the general formula E³{—Al(E³)-O—}_(c)Al(E³)₂ include alkyl groups such as methyl, ethyl,normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl andneopentyl groups. b is an integer of 2 or more, and c is an integer of 1or more. Preferably, E² and E³ are each independently a methyl group oran isobutyl group, b is 2 to 40, and C is 1 to 40.

These aluminoxanes are prepared by various methods. The methods are notparticularly limited, and they may be prepared according to methodsknown in the art. For example, a solution containing a trialkylaluminum(e.g., trimethylaluminum) dissolved in an appropriate organic solvent(e.g., benzene or aliphatic hydrocarbyl) is contacted with water toprepare the aluminoxanes. Another preparation method can involve, forexample, contacting a trialkylaluminum (e.g., trimethylaluminum) with ametal salt (e.g., copper sulfate hydrate) containing crystalline water.

In the compounds (B1) to (B3), Q¹, Q², Q³ and Q⁴ are preferably ahalogen atom or a hydrocarbyl group having 1 to 20 carbon atoms whichmay be substituted by a halogen atom. Examples of the inorganic cationin T⁺ include ferrocenium cation, alkyl-substituted ferrocenium cationsand silver cation. Examples of the organic cation in T⁺ includetriphenylmethyl cation. Examples of (BQ¹Q²Q³Q⁴)⁻ includetetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,3,4-trifluorophenyl)borate,phenyltris(pentafluorophenyl)borate andtetrakis(3,5-bistrifluoromethylphenyl)borate. Examples of the Broenstedacid represented by (L-H)⁺ include trialkyl-substituted ammonium,N,N-dialkylanilinium, dialkylammonium and triarylphosphonium.

Examples of the boron compound (B1) represented by the general formulaBQ¹Q²Q³ include tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane andphenylbis(pentafluorophenyl)borane.

Examples of the borate compound (B2) represented by the general formulaT⁺(BQ¹Q²Q³Q⁴)⁻ include ferrocenium tetrakis(pentafluorophenyl)borate,1,1′-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate,silver tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate and triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate.

Examples of the borate compound (B3) represented by the general formula(L-H)⁺(BQ¹Q²Q³Q⁴)⁻ include triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(normal butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(normal butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate,N,N-bis-trimethylsilylanilinium tetrakis(pentafluorophenyl)borate,N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate,N,N-bis-trimethylsilylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate andtri(bis-trimethylsilylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate.

<Trimerization Catalyst>

The trimerization catalyst of the present invention is a trimerizationcatalyst comprising the transition metal complex (1) and is a catalystcapable of producing 1-hexene by ethylene trimerization. For example,the transition metal complex (1) can be brought into contact with anactivating co-catalytic component to obtain a catalytic component fortrimerization.

Examples of such an activating co-catalytic component can include thecompounds (A) and (B) described above. Moreover, these compounds (A) and(B) may be used in combination.

Regarding the amount of each catalytic component used, a molar ratiobetween the compound (A) (in terms of the aluminum atom) and thetransition metal complex (1) used as a catalytic component (compound (A)(in terms of the aluminum atom)/transition metal complex (1)) is usually0.01 to 10000, preferably 5 to 5000. Also, a molar ratio between thecompound (B) and the transition metal complex (1) used as a catalyticcomponent (compound (B)/transition metal complex (1)) is usually 0.01 to100, preferably 0.5 to 10.

When each catalytic component is used in a solution state, theconcentration of the transition metal complex (1) used as a catalyticcomponent is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.The concentration of the compound (A) is usually 0.01 to 500 mmol/L,preferably 0.1 to 100 mmol/L, in terms of the aluminum atom. Theconcentration of the compound (B) is usually 0.0001 to 5 mmol/L,preferably 0.001 to 1 mmol/L.

The method for contacting each catalytic component is not particularlylimited. The transition metal complex (1) may be brought into contactwith the activating co-catalytic component to prepare a trimerizationcatalyst in advance, and then is supplied to a reactor. Alternatively,these catalytic components may be supplied to a reactor in any order andsubjected to contact treatment in the reactor.

<Process for Producing 1-Hexene>

The process for producing 1-hexene according to the present invention isa process for producing 1-hexene from ethylene and is a process forproducing 1-hexene through the trimerization reaction of ethylene.

The trimerization reaction is not particularly limited and may be, forexample, trimerization reaction using an aliphatic hydrocarbyl (e.g.,butane, pentane, hexane, heptane and octane), an aromatic hydrocarbyl(e.g., benzene and toluene), or a hydrocarbyl halide (e.g., methylenedichloride and chlorobenzene) as a solvent, trimerization reaction in aslurry state, or trimerization reaction in ethylene in a gas state canbe carried out.

The trimerization reaction can be performed by any of batch,semi-continuous and continuous process.

The pressure of ethylene is usually in the range of normal pressure to10 MPa, preferably in the range of normal pressure to 5 MPa.

The temperature of the trimerization reaction can usually be in therange of −50° C. to 220° C. and is preferably in the range of 0° C. to170° C., more preferably in the range of 50° C. to 120° C.

The time of the trimerization reaction can generally be determinedappropriately according to the reaction apparatus of interest and can bein the range of 1 minute to 20 hours.

<Catalytic Component for Olefin Polymerization>

Examples of the catalytic component for olefin polymerization used inthe present invention can include a solid catalytic component containingtitanium, magnesium and a halogen as essential ingredients; and acatalytic component comprising a metallocene transition metal complex.In addition, examples of the catalytic component for olefinpolymerization can include a complex having a phenoxyimine ligand asreported in EP0874005.

Examples of the solid catalytic component containing titanium, magnesiumand a halogen as essential ingredients can include solid catalyticcomponents described in, for example, JP 63-142008 A, JP 4-227604 A, JP5-339319 A, JP 6-179720 A, JP 9-31119 A, JP 11-80234 A, JP 11-322833 Aor the like.

Examples of the catalytic component for olefin polymerization comprisinga transition metal complex containing metallocene can include atransition metal complex represented by the following general formula(2):

wherein M² represents a transition metal atom of Group 4 of the PeriodicTable of the Elements; Cp¹ represents a group having acyclopentadiene-type anionic skeleton; J¹ represents a group linking Cp¹and D¹ by one or two atoms of Group 14 of the Periodic Table of theElements; q represents 0 or 1; when q is 1, D¹ represents a group havinga cyclopentadiene-type anionic skeleton or a group which links J¹ and M²and which is bonded to M² at its atom of Group 15 or 16 of the PeriodicTable of the Elements, and when q is 0, D¹ represents a group having acyclopentadiene-type anionic skeleton; andX⁴ and X⁵ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20.

Preferable examples of the catalytic component for olefin polymerizationcan include transition metal complexes represented by the followinggeneral formulas (3), (4) or (5):

wherein M³ represents a transition metal atom of Group 4 of the PeriodicTable of the Elements; Cp² and Cp³ represent a group having acyclopentadiene-type anionic skeleton; J² represents a group linking Cp²and Cp³ by one or two atoms of Group 14 of the Periodic Table of theElements; andX⁶ and X⁷ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20,

wherein M⁴ represents a transition metal atom of Group 4 of the PeriodicTable of the Elements; Cp⁴ represents a group having acyclopentadiene-type anionic skeleton; J³ represents a group linking Cp⁴and A¹ by one or two atoms of Group 14 of the Periodic Table of theElements; A¹ represents a group which links J³ and M⁴ and which isbonded to M⁴ at its atom of Group 15 or 16 of the Periodic Table of theElements; and

X⁸ and X⁹ each independently represent

a hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, and

whereinM⁵ represents a transition metal atom of Group 4 of the Periodic Tableof the Elements;A² represents an atom of Group 16 of the Periodic Table of the Elements;J⁴ represents an atom of Group 14 of the Periodic Table of the Elements;Cp⁵ represents a group having a cyclopentadiene-type anionic skeleton;X¹⁰, X¹¹, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ each independently representa hydrogen atom, a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20; andR¹⁸ and R¹⁹ each independently representa hydrogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20;of R¹⁴, R¹⁵, R¹⁶ and R¹⁷, two groups bonded to two adjacent carbon atomsmay be bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded; X¹⁰ and X¹¹ may be bonded toeach other to form a ring together with M⁵; and R¹⁸ and R¹⁹ may bebonded to each other to form a ring together with J⁴.

The transition metal complex represented by the general formula (2) willbe described in detail.

Examples of the transition metal atom of Group 4 of the Periodic Tableof the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised,1989) in M² include titanium, zirconium and hafnium atoms, for example.

Examples of the group having a cyclopentadiene-type anionic skeleton,represented by Cp¹ or D¹ include η⁵-cyclopentadienyl,η⁵-methylcyclopentadienyl, η⁵-dimethylcyclopentadienyl,η⁵-trimethylcyclopentadienyl, η⁵-tetramethylcyclopentadienyl,η⁵-ethylcyclopentadienyl, η⁵-n-propylcyclopentadienyl,η⁵-isopropylcyclopentadienyl, η⁵-n-butylcyclopentadienyl,η⁵-sec-butylcyclopentadienyl, η⁵-tert-butylcyclopentadienyl,η⁵-n-pentylcyclopentadienyl, η⁵-neopentylcyclopentadienyl,η⁵-n-hexylcyclopentadienyl, η⁵-n-octylcyclopentadienyl,η⁵-phenylcyclopentadienyl, η⁵-naphthylcyclopentadienyl,η⁵-trimethylsilylcyclopentadienyl, η⁵-triethylsilylcyclopentadienyl,η⁵-tert-butyldimethylsilylcyclopentadienyl, η⁵-indenyl,η⁵-methylindenyl, η⁵-dimethylindenyl, η⁵-ethylindenyl,η⁵-n-propylindenyl, η⁵-isopropylindenyl, η⁵-n-butylindenyl,η⁵-sec-butylindenyl, η⁵-tert-butylindenyl, η⁵-n-pentylindenyl,η⁵-neopentylindenyl, η⁵-n-hexylindenyl, η⁵-n-octylindenyl,η⁵-n-decylindenyl, η⁵-phenylindenyl, η⁵-methylphenylindenyl,η⁵-naphthylindenyl, η⁵-trimethylsilylindenyl, η⁵-triethylsilylindenyl,η⁵-tert-butyldimethylsilylindenyl, η⁵-tetrahydroindenyl, η⁵-fluorenyl,η⁵-methylfluorenyl, η⁵-dimethylfluorenyl, η⁵-ethylfluorenyl,η⁵-diethylfluorenyl, η⁵-n-propylfluorenyl, η⁵-di-n-propylfluorenyl,η⁵-isopropylfluorenyl, η⁵-diisopropylfluorenyl, η⁵-n-butylfluorenyl,η⁵-sec-butylfluorenyl, η⁵-tert-butylfluorenyl, η⁵-di-n-butylfluorenyl,η⁵-di-sec-butylfluorenyl, η⁵-di-tert-butylfluorenyl,η⁵-n-pentylfluorenyl, η⁵-neopentylfluorenyl, η⁵-n-hexylfluorenyl,η⁵-n-octylfluorenyl, η⁵-n-decylfluorenyl, η⁵-n-dodecylfluorenyl,η⁵-phenylfluorenyl, η⁵-di-phenylfluorenyl, η⁵-methylphenylfluorenyl,η⁵-naphthylfluorenyl, η⁵-trimethylsilylfluorenyl,η⁵-bis-trimethylsilylfluorenyl, η⁵-triethylsilylfluorenyl,η⁵-tert-butyldimethylsilylfluorenyl and η⁵-azulenyl groups.η⁵-cyclopentadienyl, η⁵-methylcyclopentadienyl,η⁵-tert-butylcyclopentadienyl, η⁵-tetramethylcyclopentadienyl,η⁵-indenyl, η⁵-fluorenyl and η⁵-azulenyl groups, etc. are preferable.

J¹ is a group linking Cp¹ and D¹ by one or two atoms of Group 14 of thePeriodic Table of the Elements. J¹ is —SiR₂—, —CR₂—, —SiR₂SiR₂—,—CR₂CR₂—, —CR═CR—, —CR₂SiR₂— or —GeR₂—. R is a hydrogen atom, an alkylgroup having up to 20 carbon atoms which may have a halogen atom as asubstituent, an aralkyl group having up to 20 carbon atoms which mayhave a halogen atom as a substituent, an aryl group having up to 20carbon atoms which may have a halogen atom as a substituent or ahydrocarbyl-substituted silyl group having up to 20 carbon atoms whichmay have a halogen atom as a substituent. R groups may be the same ordifferent.

Examples of R include: alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups;aralkyl groups such as benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups;aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups;hydrocarbyl-substituted silyl groups such as methylsilyl, ethylsilyl,phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups; and groups obtained bysubstituting some or all of hydrogen atoms in these groups by a halogenatom. J¹ is preferably —SiR₂—, —CR₂— or —CR₂CR₂—, and R is preferably ahydrogen atom or a methyl group.

The group which links J¹ and M² and which is bonded to M² at its atom ofGroup 15 or 16 of the Periodic Table of the Elements, represented by D¹is, for example, —O—, —S—, —NR— or —PR—, preferably —NR—. R is ahydrogen atom, an alkyl group having up to 20 carbon atoms which mayhave a halogen atom as a substituent, an aralkyl group having up to 20carbon atoms which may have a halogen atom as a substituent, an arylgroup having up to 20 carbon atoms which may have a halogen atom as asubstituent or a hydrocarbyl-substituted silyl group having up to 20carbon atoms which may have a halogen atom as a substituent.

Examples of R include: alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups;aralkyl groups such as benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups;aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups;hydrocarbyl-substituted silyl groups such as methylsilyl, ethylsilyl,phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups; and groups obtained bysubstituting some or all of hydrogen atoms in these groups by a halogenatom. R is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl,norbornyl, benzyl or phenyl group, etc.

Furthermore, examples of the group which links J¹ and M² and which isbonded to M² at its atom of Group 15 or 16 of the Periodic Table of theElements, represented by D¹ include groups represented by the followinggeneral formulas (2-1), (2-2), (2-3) and (2-4):

The general formula (2-1) is preferable. R is a hydrogen atom, an alkylgroup having up to 20 carbon atoms which may have a halogen atom as asubstituent, an aralkyl group having up to 20 carbon atoms which mayhave a halogen atom as a substituent, an aryl group having up to 20carbon atoms which may have a halogen atom as a substituent or ahydrocarbyl-substituted silyl group having up to 20 carbon atoms whichmay have a halogen atom as a substituent. Examples of R include: alkylgroups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl,n-dodecyl, n-pentadecyl and n-eicosyl groups; aralkyl groups such asbenzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups;aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups;hydrocarbyl-substituted silyl groups such as methylsilyl, ethylsilyl,phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups; and groups obtained bysubstituting some or all of hydrogen atoms in these groups by a halogenatom. R is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl,norbornyl, benzyl or phenyl group, etc.

Moreover, a hydrogen atom on the benzene ring in the general formulas(2-1), (2-2), (2-3) and (2-4) may be substituted with

a halogen atom,an alkyl group having 1 to 20 carbon atoms which may have a halogen atomas a substituent,an alkoxy group having 1 to 20 carbon atoms which may have a halogenatom as a substituent,an aryl group having 6 to 20 carbon atoms which may have a halogen atomas a substituent,an aryloxy group having 6 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyl group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,an aralkyloxy group having 7 to 20 carbon atoms which may have a halogenatom as a substituent,a substituted silyl group represented by —Si(R¹²)₃, wherein the threeR¹² groups each independently represent a hydrogen atom, a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in the three R¹² groups is 1 to 20, ora disubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20.

Examples of the halogen atom in X⁴, X⁵ and the substituent on thebenzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4)include fluorine, chlorine, bromine and iodine atoms.

Examples of the alkyl group having 1 to 20 carbon atoms in X⁴, X⁵ andthe substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4) include methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl,n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkyl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkyl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the alkyl group having 1 to 20carbon atoms having a halogen atom as a substituent includefluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl,difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl,chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl,pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl,tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl,perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl,perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl,perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl,perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl,perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl,perbromopentadecyl and perbromoeicosyl groups.

Examples of the aryl group having 6 to 20 carbon atoms in X⁴, X⁵ and thesubstituent on the benzene ring in the general formulas (2-1), (2-2),(2-3) and (2-4) include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the aryl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the aryl group having 6 to 20carbon atoms having a halogen atom as a substituent includefluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl,pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.

Examples of the aralkyl group having 7 to 20 carbon atoms in X⁴, X⁵ andthe substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4) include benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups.

Any of these aralkyl groups may be substituted by a halogen atom.Examples of the halogen atom include fluorine, chlorine, bromine andiodine atoms.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyl group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyl group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkylgroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all hydrogen atoms inthe aralkyl group by a halogen atom.

Examples of the alkoxy group having 1 to 20 carbon atoms in X⁴, X⁵ andthe substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4) include methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy,n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkoxy group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkoxy group may be substitutedwith a halogen atom. Examples of the halogen atom include fluorine,chlorine, bromine and iodine atoms. Examples of the alkoxy group having1 to 20 carbon atoms having a halogen atom as a substituent includegroups obtained by substituting some or all hydrogen atoms in the alkoxygroup by a halogen atom.

Examples of the aryloxy group having 6 to 20 carbon atoms in X⁴, X⁵ andthe substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4) include aryloxy groups having 6 to 20 carbonatoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy,4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy,2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy,3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy,2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy,3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy,2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy,pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy,n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy,n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy andanthracenoxy groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aryloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aryloxygroup having 6 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all hydrogen atoms inthe aryloxy group by a halogen atom.

Examples of the aralkyloxy group having 7 to 20 carbon atoms in X⁴, X⁵and the substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4) include benzyloxy, (2-methylphenyl)methoxy,(3-methylphenyl)methoxy, (4-methylphenyl)methoxy,(2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy,(2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy,(3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy,(2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy,(2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy,(2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy,(2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy,(2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy,(ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy,(n-butylphenyl)methoxy, (sec-butylphenyl)methoxy,(tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy,(n-octylphenyl)methoxy, (n-decylphenyl)methoxy,(n-tetradecylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxygroups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkyloxygroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all hydrogen atoms inthe aralkyloxy group by a halogen atom.

In the substituted silyl group represented by —Si(R¹²)₃, wherein thethree R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, in X⁴, X⁵and the substituent on the benzene ring in the general formulas (2-1),(2-2), (2-3) and (2-4), the R¹² groups are each independently a hydrogenatom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbonatoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl,n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); ora halogenated hydrocarbyl group obtained by substituting some or allhydrogen atoms in the hydrocarbyl group by a halogen atom, and the totalnumber of the carbon atoms in the three R¹² groups is in the range of 1to 20. The total number of the carbon atoms in these three R¹² groups ispreferably in the range of 3 to 18. Specific examples of the substitutedsilyl group include: monosubstituted silyl groups having one hydrocarbylor halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl andphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in the hydrocarbyl groups of these groups by a halogenatom; disubstituted silyl groups having two hydrocarbyl and/orhydrocarbyl halide groups, such as dimethylsilyl, diethylsilyl anddiphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in the hydrocarbyl groups of these groups by a halogenatom; and trisubstituted silyl groups having three hydrocarbyl and/orhydrocarbyl halide groups, such as trimethylsilyl, triethylsilyl,tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups, and groups obtained bysubstituting some or all hydrogen atoms in the hydrocarbyl groups ofthese groups by a halogen atom. Of them, trisubstituted silyl groups arepreferable, and trimethylsilyl, tert-butyldimethylsilyl andtriphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in these groups by a halogen atom are more preferable.

In the disubstituted amino group represented by —N(R¹³)₂, wherein thetwo R¹³ groups each independently represent a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the two R¹³ groups is 2 to 20, in X⁴, X⁵ and the substituent on thebenzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4), theR¹³ groups each independently represent a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the two R¹³ groups is in the range of 2 to 20, more preferably in therange of 2 to 10. The hydrocarbyl group and the halogenated hydrocarbylgroup are the same as those described as a hydrocarbyl group and ahalogenated hydrocarbyl group for the substituted silyl group. Moreover,these two R¹³ groups may be bonded to each other to form a ring togetherwith the nitrogen atom to which the two R¹³ groups are bonded. Examplesof such a disubstituted amino group include dimethylamino, diethylamino,di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino,di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino,di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino,bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl,pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl anddihydroisoindolyl groups, and groups obtained by substituting some orall hydrogen atoms in these groups by a halogen atom. Of them,dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, andgroups obtained by substituting some or all hydrogen atoms in thesegroups by a halogen atom are preferable.

The transition metal complex represented by the general formula (2) ispreferably a complex wherein q is 1, more preferably wherein q is 1, andD¹ is a group binding to M² by a nitrogen atom or a group represented bythe general formula (2-1), even more preferably wherein q is 1, and D¹is a group represented by the general formula (2-1).

The transition metal complexes represented by the general formulas (3)and (4) will be described in detail.

Examples of the transition metal atom of Group 4 of the Periodic Tableof the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised,1989) in M³ include titanium, zirconium and hafnium atoms. Zirconium andhafnium atoms are preferable.

Examples of the transition metal atom of Group 4 of the Periodic Tableof the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised,1989) in M⁴ include titanium, zirconium and hafnium atoms. Titanium andzirconium atoms are preferable.

A¹ is a group linking J³ and M⁴ by an oxygen, sulfur, nitrogen orphosphorus atom. A¹ is, for example, —O—, —S—, —NR— or —PR—, preferably—NR—. However, R is a hydrogen atom, an alkyl group having up to 20carbon atoms which may have a halogen atom as a substituent, an aralkylgroup having up to 20 carbon atoms which may have a halogen atom as asubstituent, an aryl group having up to 20 carbon atoms which may have ahalogen atom as a substituent or a hydrocarbyl-substituted silyl grouphaving up to 20 carbon atoms which may have a halogen atom as asubstituent.

Examples of R include: alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups;aralkyl groups such as benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups;aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups;hydrocarbyl-substituted silyl groups such as methylsilyl, ethylsilyl,phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups; and groups obtained bysubstituting some or all hydrogen atoms in these groups by a halogenatom. R is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl,norbornyl, benzyl or phenyl group, etc.

J² is a group linking Cp² and Cp³ by one or two atoms of Group 14 of thePeriodic Table of the Elements, and J³ is a group linking Cp⁴ and A¹ byone or two atoms of Group 14 of the Periodic Table of the Elements. J²and J³ are each independently —SiR₂—, —CR₂—, —SiR₂SiR₂—, —CR₂CR₂—,—CR═CR—, —CR₂SiR₂— or —GeR₂—. However, R is a hydrogen atom, an alkylgroup having up to 20 carbon atoms which may have a halogen atom as asubstituent, an aralkyl group having up to 20 carbon atoms which mayhave a halogen atom as a substituent, an aryl group having up to 20carbon atoms which may have a halogen atom as a substituent or ahydrocarbyl-substituted silyl group having up to 20 carbon atoms whichmay have a halogen atom as a substituent. A plurality of R moieties maybe the same or different.

Examples of R include: alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups;aralkyl groups such as benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups;aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups;hydrocarbyl-substituted silyl groups such as methylsilyl, ethylsilyl,phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups; and groups obtained bysubstituting some or all hydrogen atoms in these groups by a halogenatom. J² and J³ are preferably —SiR₂—, —CR₂— or —CR₂CR₂—, and R ispreferably a hydrogen atom or a methyl group.

Examples of the group having a cyclopentadiene-type anionic skeletonrepresented by the substituents Cp², Cp³ and Cp⁴ includeη⁵-cyclopentadienyl, η⁵-methylcyclopentadienyl,η⁵-dimethylcyclopentadienyl, η⁵-trimethylcyclopentadienyl,η⁵-tetramethylcyclopentadienyl, η⁵-ethylcyclopentadienyl,η⁵-n-propylcyclopentadienyl, η⁵-isopropylcyclopentadienyl,η⁵-n-butylcyclopentadienyl, η⁵-sec-butylcyclopentadienyl,η⁵-tert-butylcyclopentadienyl, η⁵-n-pentylcyclopentadienyl,η⁵-neopentylcyclopentadienyl, η⁵-n-hexylcyclopentadienyl,η⁵-n-octylcyclopentadienyl, η⁵-phenylcyclopentadienyl,η⁵-naphthylcyclopentadienyl, η⁵-trimethylsilylcyclopentadienyl,η⁵-triethylsilylcyclopentadienyl,η⁵-tert-butyldimethylsilylcyclopentadienyl, η⁵-indenyl,η⁵-methylindenyl, η⁵-dimethylindenyl, η⁵-ethylindenyl,η⁵-n-propylindenyl, η⁵-isopropylindenyl, η⁵-n-butylindenyl,η⁵-sec-butylindenyl, η⁵-tert-butylindenyl, η⁵-n-pentylindenyl,η⁵-neopentylindenyl, η⁵-n-hexylindenyl, η⁵-n-octylindenyl,η⁵-n-decylindenyl, η⁵-phenylindenyl, η⁵-methylphenylindenyl,η⁵-naphthylindenyl, η⁵-trimethylsilylindenyl, η⁵-triethylsilylindenyl,η⁵-tert-butyldimethylsilylindenyl, η⁵-tetrahydroindenyl, η⁵-fluorenyl,η⁵-methylfluorenyl, η⁵-dimethylfluorenyl, η⁵-ethylfluorenyl,η⁵-diethylfluorenyl, η⁵-n-propylfluorenyl, η⁵-di-n-propylfluorenyl,η⁵-isopropylfluorenyl, η⁵-diisopropylfluorenyl, η⁵-n-butylfluorenyl,η⁵-sec-butylfluorenyl, η⁵-tert-butylfluorenyl, η⁵-di-n-butylfluorenyl,η⁵-di-sec-butylfluorenyl, η⁵-di-tert-butylfluorenyl,η⁵-n-pentylfluorenyl, η⁵-neopentylfluorenyl, η⁵-n-hexylfluorenyl,η⁵-n-octylfluorenyl, η⁵-n-decylfluorenyl, η⁵-n-dodecylfluorenyl,η⁵-phenylfluorenyl, η⁵-di-phenylfluorenyl, η⁵-methylphenylfluorenyl,η⁵-naphthylfluorenyl, η⁵-trimethylsilylfluorenyl,η⁵-bis-trimethylsilylfluorenyl, η⁵-triethylsilylfluorenyl,η⁵-tert-butyldimethylsilylfluorenyl and η⁵-azulenyl groups.η⁵-cyclopentadienyl, η⁵-methylcyclopentadienyl,η⁵-tert-butylcyclopentadienyl, η⁵-tetramethylcyclopentadienyl,η⁵-indenyl, η⁵-fluorenyl and η⁵-azulenyl groups, etc. are preferable.

Examples of the halogen atom in X⁶, X⁷, X⁸ and X⁹ include fluorine,chlorine, bromine and iodine atoms.

Examples of the alkyl group having 1 to 20 carbon atoms in X⁶, X⁷, X⁸and X⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl,n-dodecyl, n-pentadecyl and n-eicosyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkyl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkyl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the alkyl group having 1 to 20carbon atoms having a halogen atom as a substituent includefluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl,difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl,chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl,pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl,tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl,perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl,perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl,perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl,perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl,perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl,perbromopentadecyl and perbromoeicosyl groups.

Examples of the aryl group having 6 to 20 carbon atoms in X⁶, X⁷, X⁸ andX⁹ include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the aryl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the aryl group having 6 to 20carbon atoms having a halogen atom as a substituent includefluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl,pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.

Examples of the aralkyl group having 7 to 20 carbon atoms in X⁶, X⁷, X⁸and X⁹ include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups.

Any of these aralkyl groups may be substituted by a halogen atom.Examples of the halogen atom include fluorine, chlorine, bromine andiodine atoms.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyl group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyl group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkylgroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aralkyl group with a halogen atom.

Examples of the alkoxy group having 1 to 20 carbon atoms in X⁶, X⁷, X⁸and X⁹ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy,n-dodecoxy, n-pentadecoxy and n-eicosoxy.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkoxy group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkoxy group may be substitutedwith a halogen atom. Examples of the halogen atom include fluorine,chlorine, bromine and iodine atoms. Examples of the alkoxy group having1 to 20 carbon atoms having a halogen atom as a substituent includegroups obtained by substituting some or all of hydrogen atoms in thealkoxy group with a halogen atom.

Examples of the aryloxy group having 6 to 20 carbon atoms in X⁶, X⁷, X⁸and X⁹ include aryloxy groups having 6 to 20 carbon atoms, such asphenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy,2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy,2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy,2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy,n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy,tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy,n-tetradecylphenoxy, naphthoxy and anthracenoxy groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aryloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aryloxygroup having 6 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aryloxy group with a halogen atom.

Examples of the aralkyloxy group having 7 to 20 carbon atoms in X⁶, X⁷,X⁸ and X⁹ include benzyloxy, (2-methylphenyl)methoxy,(3-methylphenyl)methoxy, (4-methylphenyl)methoxy,(2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy,(2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy,(3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy,(2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy,(2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy,(2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy,(2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy,(2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy,(ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy,(n-butylphenyl)methoxy, (sec-butylphenyl)methoxy,(tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy,(n-octylphenyl)methoxy, (n-decylphenyl)methoxy,(n-tetradecylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxygroups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkyloxygroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aralkyloxy group with a halogen atom.

In the substituted silyl group represented by —Si(R¹²)₃, wherein thethree R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, in X⁶,X⁷, X⁸ and X⁹, the R¹² groups are each independently a hydrogen atom; ahydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms(e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl,n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); ora halogenated hydrocarbyl group obtained by substituting some or allhydrogen atoms in the hydrocarbyl group by a halogen atom, and the totalnumber of the carbon atoms in the three R¹² groups is in the range of 1to 20. The total number of the carbon atoms in these three R¹² groups ispreferably in the range of 3 to 18. Specific examples of the substitutedsilyl group include: monosubstituted silyl groups having one hydrocarbylor halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl andphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in the hydrocarbyl groups of these groups by a halogenatom; disubstituted silyl groups having two hydrocarbyl and/orhalogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl anddiphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in the hydrocarbyl groups of these groups by a halogenatom; and trisubstituted silyl groups having three hydrocarbyl and/orhalogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl,tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl groups, and groups obtained bysubstituting some or all hydrogen atoms in the hydrocarbyl groups ofthese groups by a halogen atom. Of them, trisubstituted silyl groups arepreferable, and trimethylsilyl, tert-butyldimethylsilyl andtriphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in these groups by a halogen atom are more preferable.

In the disubstituted amino group represented by —N(R¹³)₂, wherein thetwo R¹³ groups each independently represent a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the two R¹³ groups is 2 to 20, in X⁶, X⁷, X⁸ and X⁹, the R¹³ groupseach independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is in the range of 2 to 20, more preferably in the range of 2to 10. The hydrocarbyl group and the halogenated hydrocarbyl group arethe same as those described as a hydrocarbyl group and a halogenatedhydrocarbyl group for the substituted silyl group. Moreover, these twoR¹³ groups may be bonded to each other to form a ring together with thenitrogen atom to which the two R¹³ groups are bonded thereto. Examplesof such a disubstituted amino group include dimethylamino, diethylamino,di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino,di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino,di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino,bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl,pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl anddihydroisoindolyl groups, and groups obtained by substituting some orall hydrogen atoms in these groups by a halogen atom. Of them,dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, andgroups obtained by substituting some or all hydrogen atoms in thesegroups by a halogen atom are preferable.

The transition metal complex represented by the general formula (3) canbe produced, for example, by a method described in JP 3290218B.

Examples of the complex represented by the general formula (3) includemethylenebis(cyclopentadienyl)zirconium dichloride,isopropylidenebis(cyclopentadienyl)zirconium dichloride,diphenylmethylenebis(cyclopentadienyl)zirconium dichloride,1,2-ethylene-bis(cyclopentadienyl)zirconium dichloride,dimethylsilylenebis(cyclopentadienyl)zirconium dichloride,diphenylsilylenebis(cyclopentadienyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(cyclopentadienyl)zirconium dichloride,

methylenebis(methylcyclopentadienyl)zirconium dichloride,isopropylidenebis(methylcyclopentadienyl)zirconium dichloride,diphenylmethylenebis(methylcyclopentadienyl)zirconium dichloride,1,2-ethylene-bis(methylcyclopentadienyl)zirconium dichloride,dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,diphenylsilylenebis(methylcyclopentadienyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(methylcyclopentadienyl)zirconiumdichloride,

methylenebis(n-butylcyclopentadienyl)zirconium dichloride,isopropylidenebis(n-butylcyclopentadienyl)zirconium dichloride,diphenylmethylenebis(n-butylcyclopentadienyl)zirconium dichloride,1,2-ethylene-bis(n-butylcyclopentadienyl)zirconium dichloride,dimethylsilylenebis(n-butylcyclopentadienyl)zirconium dichloride,diphenylsilylenebis(n-butylcyclopentadienyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(n-butylcyclopentadienyl)zirconiumdichloride,

methylenebis(tert-butylcyclopentadienyl)zirconium dichloride,isopropylidenebis(tert-butylcyclopentadienyl)zirconium dichloride,diphenylmethylenebis(tert-butylcyclopentadienyl)zirconium dichloride,1,2-ethylene-bis(tert-butylcyclopentadienyl)zirconium dichloride,dimethylsilylenebis(tert-butylcyclopentadienyl)zirconium dichloride,diphenylsilylenebis(tert-butylcyclopentadienyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(tert-butylcyclopentadienyl)zirconiumdichloride,

methylenebis(tetramethylcyclopentadienyl)zirconium dichloride,isopropylidenebis(tetramethylcyclopentadienyl)zirconium dichloride,diphenylmethylenebis(tetramethylcyclopentadienyl)zirconium dichloride,1,2-ethylene-bis(tetramethylcyclopentadienyl)zirconium dichloride,dimethylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride,diphenylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(tetramethylcyclopentadienyl)zirconiumdichloride,

methylenebis(indenyl)zirconium dichloride,isopropylidenebis(indenyl)zirconium dichloride,diphenylmethylenebis(indenyl)zirconium dichloride,1,2-ethylene-bis(indenyl)zirconium dichloride,dimethylsilylenebis(indenyl)zirconium dichloride,diphenylsilylenebis(indenyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(indenyl)zirconium dichloride,

methylenebis(fluorenyl)zirconium dichloride,isopropylidenebis(fluorenyl)zirconium dichloride,diphenylmethylenebis(fluorenyl)zirconium dichloride,1,2-ethylene-bis(fluorenyl)zirconium dichloride,dimethylsilylenebis(fluorenyl)zirconium dichloride,diphenylsilylenebis(fluorenyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(fluorenyl)zirconium dichloride,

methylenebis(azulenyl)zirconium dichloride,isopropylidenebis(azulenyl)zirconium dichloride,diphenylmethylenebis(azulenyl)zirconium dichloride,1,2-ethylene-bis(azulenyl)zirconium dichloride,dimethylsilylenebis(azulenyl)zirconium dichloride,diphenylsilylenebis(azulenyl)zirconium dichloride,1,2-tetramethyldisilylene-bis(azulenyl)zirconium dichloride,

methylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,isopropylidenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,diphenylmethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,1,2-ethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,diphenylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,1,2-tetramethyldisilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconiumdichloride,

methylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,1,2-ethylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,dimethylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,diphenylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,

methylene(cyclopentadienyl)(indenyl)zirconium dichloride,isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,diphenylmethylene(cyclopentadienyl)(indenyl)zirconium dichloride,1,2-ethylene-(cyclopentadienyl)(indenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride,diphenylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(indenyl)zirconiumdichloride,

methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,1,2-ethylene-(cyclopentadienyl)(fluorenyl)zirconium dichloride,dimethylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(fluorenyl)zirconiumdichloride,

methylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,1,2-ethylene-(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,dimethylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,1,2-tetramethyldisilylene-(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,

methylenebis(cyclopentadienyl)hafnium dichloride,isopropylidenebis(cyclopentadienyl)hafnium dichloride,diphenylmethylenebis(cyclopentadienyl)hafnium dichloride,1,2-ethylene-bis(cyclopentadienyl)hafnium dichloride,dimethylsilylenebis(cyclopentadienyl)hafnium dichloride,diphenylsilylenebis(cyclopentadienyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(cyclopentadienyl)hafnium dichloride,

methylenebis(methylcyclopentadienyl)hafnium dichloride,isopropylidenebis(methylcyclopentadienyl)hafnium dichloride,diphenylmethylenebis(methylcyclopentadienyl)hafnium dichloride,1,2-ethylene-bis(methylcyclopentadienyl)hafnium dichloride,dimethylsilylenebis(methylcyclopentadienyl)hafnium dichloride,diphenylsilylenebis(methylcyclopentadienyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(methylcyclopentadienyl)hafnium dichloride,

methylenebis(n-butylcyclopentadienyl)hafnium dichloride,isopropylidenebis(n-butylcyclopentadienyl)hafnium dichloride,diphenylmethylenebis(n-butylcyclopentadienyl)hafnium dichloride,1,2-ethylene-bis(n-butylcyclopentadienyl)hafnium dichloride,dimethylsilylenebis(n-butylcyclopentadienyl)hafnium dichloride,diphenylsilylenebis(n-butylcyclopentadienyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(n-butylcyclopentadienyl)hafniumdichloride,

methylenebis(tert-butylcyclopentadienyl)hafnium dichloride,isopropylidenebis(tert-butylcyclopentadienyl)hafnium dichloride,diphenylmethylenebis(tert-butylcyclopentadienyl)hafnium dichloride,1,2-ethylene-bis(tert-butylcyclopentadienyl)hafnium dichloride,dimethylsilylenebis(tert-butylcyclopentadienyl)hafnium dichloride,diphenylsilylenebis(tert-butylcyclopentadienyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(tert-butylcyclopentadienyl)hafniumdichloride,

methylenebis(tetramethylcyclopentadienyl)hafnium dichloride,isopropylidenebis(tetramethylcyclopentadienyl)hafnium dichloride,diphenylmethylenebis(tetramethylcyclopentadienyl)hafnium dichloride,1,2-ethylene-bis(tetramethylcyclopentadienyl)hafnium dichloride,dimethylsilylenebis(tetramethylcyclopentadienyl)hafnium dichloride,diphenylsilylenebis(tetramethylcyclopentadienyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(tetramethylcyclopentadienyl)hafniumdichloride,

methylenebis(indenyl)hafnium dichloride,isopropylidenebis(indenyl)hafnium dichloride,diphenylmethylenebis(indenyl)hafnium dichloride,1,2-ethylene-bis(indenyl)hafnium dichloride,dimethylsilylenebis(indenyl)hafnium dichloride,diphenylsilylenebis(indenyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(indenyl)hafnium dichloride,

methylenebis(fluorenyl)hafnium dichloride,isopropylidenebis(fluorenyl)hafnium dichloride,diphenylmethylenebis(fluorenyl)hafnium dichloride,1,2-ethylene-bis(fluorenyl)hafnium dichloride,dimethylsilylenebis(fluorenyl)hafnium dichloride,diphenylsilylenebis(fluorenyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(fluorenyl)hafnium dichloride,

methylenebis(azulenyl)hafnium dichloride,isopropylidenebis(azulenyl)hafnium dichloride,diphenylmethylenebis(azulenyl)hafnium dichloride,1,2-ethylene-bis(azulenyl)hafnium dichloride,dimethylsilylenebis(azulenyl)hafnium dichloride,diphenylsilylenebis(azulenyl)hafnium dichloride,1,2-tetramethyldisilylene-bis(azulenyl)hafnium dichloride,

methylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,isopropylidenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,diphenylmethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,1,2-ethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,diphenylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,1,2-tetramethyldisilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride,

methylene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,1,2-ethylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,dimethylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,diphenylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)hafniumdichloride,

methylene(cyclopentadienyl)(indenyl)hafnium dichloride,isopropylidene(cyclopentadienyl)(indenyl)hafnium dichloride,diphenylmethylene(cyclopentadienyl)(indenyl)hafnium dichloride,1,2-ethylene-(cyclopentadienyl)(indenyl)hafnium dichloride,dimethylsilylene(cyclopentadienyl)(indenyl)hafnium dichloride,diphenylsilylene(cyclopentadienyl)(indenyl)hafnium dichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(indenyl)hafnium dichloride,

methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,isopropylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,1,2-ethylene-(cyclopentadienyl)(fluorenyl)hafnium dichloride,dimethylsilylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,diphenylsilylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,1,2-tetramethyldisilylene-(cyclopentadienyl)(fluorenyl)hafniumdichloride,

methylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,1,2-ethylene-(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,dimethylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,diphenylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride,1,2-tetramethyldisilylene-(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride, and compounds obtained by replacing zirconium or hafnium inthese compounds with titanium; replacing cyclopentadienyl therein withmethylcyclopentadienyl, n-butylcyclopentadienyl,t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl orfluorenyl; or replacing chloride therein with bromide, iodide, hydride,methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide,benzyloxide, dimethylamide or diethylamide.

The transition metal complex represented by the general formula (4) canbe produced, for example, by a method described in JP 2535249B.

Examples of the complex represented by the general formula (4) includemethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,methylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,methylene(phenylamido)(cyclopentadienyl)titanium dichloride,methylene(benzylamido)(cyclopentadienyl)titanium dichloride,methylene(tert-butylphosphido)(cyclopentadienyl)titanium dichloride,methylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,methylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,methylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,

isopropylidene(tert-butylamido)(cyclopentadienyl)titanium dichloride,isopropylidene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,isopropylidene(phenylamido)(cyclopentadienyl)titanium dichloride,isopropylidene(benzylamido)(cyclopentadienyl)titanium dichloride,isopropylidene(tert-butylphosphido)(cyclopentadienyl)titaniumdichloride,isopropylidene(cyclohexylphosphido)(cyclopentadienyl)titaniumdichloride, isopropylidene(phenylphosphido)(cyclopentadienyl)titaniumdichloride, isopropylidene(benzylphosphido)(cyclopentadienyl)titaniumdichloride,

diphenylmethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,diphenylmethylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,diphenylmethylene(phenylamido)(cyclopentadienyl)titanium dichloride,diphenylmethylene(benzylamido)(cyclopentadienyl)titanium dichloride,diphenylmethylene(tert-butylphosphido)(cyclopentadienyl)titaniumdichloride,diphenylmethylene(cyclohexylphosphido)(cyclopentadienyl)titaniumdichloride, diphenylmethylene(phenylphosphido)(cyclopentadienyl)titaniumdichloride, diphenylmethylene(benzylphosphido)(cyclopentadienyl)titaniumdichloride,

1,2-ethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(phenylamido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(benzylamido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(tert-butylphosphido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,1,2-ethylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,

dimethylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,dimethylsilylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,dimethylsilylene(phenylamido)(cyclopentadienyl)titanium dichloride,dimethylsilylene(benzylamido)(cyclopentadienyl)titanium dichloride,dimethylsilylene(tert-butylphosphido)(cyclopentadienyl)titaniumdichloride,dimethylsilylene(cyclohexylphosphido)(cyclopentadienyl)titaniumdichloride, dimethylsilylene(phenylphosphido)(cyclopentadienyl)titaniumdichloride, dimethylsilylene(benzylphosphido)(cyclopentadienyl)titaniumdichloride,

diphenylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,diphenylsilylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,diphenylsilylene(phenylamido)(cyclopentadienyl)titanium dichloride,diphenylsilylene(benzylamido)(cyclopentadienyl)titanium dichloride,diphenylsilylene(tert-butylphosphido)(cyclopentadienyl)titaniumdichloride,diphenylsilylene(cyclohexylphosphido)(cyclopentadienyl)titaniumdichloride, diphenylsilylene(phenylphosphido)(cyclopentadienyl)titaniumdichloride, diphenylsilylene(benzylphosphido)(cyclopentadienyl)titaniumdichloride,

1,2-tetramethyldisilylene(tert-butylamido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(cyclohexylamido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(phenylamido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(benzylamido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(tert-butylphosphido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(cyclohexylphosphido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(phenylphosphido)(cyclopentadienyl)titaniumdichloride,1,2-tetramethyldisilylene(benzylphosphido)(cyclopentadienyl)titaniumdichloride, and compounds obtained by replacing titanium in thesecompounds with zirconium or hafnium; replacing cyclopentadienyl thereinwith methylcyclopentadienyl, n-butylcyclopentadienyl,t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl orfluorenyl; replacing t-butylamido therein with an oxygen or sulfur atom;or replacing chloride therein with bromide, iodide, hydride, methyl,phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide,benzyloxide, dimethylamide or diethylamide.

The complex represented by the general formula (5) will be described indetail. Examples of the transition metal atom of Group 4 of the PeriodicTable of the Elements (IUPAC Nomenclature of Inorganic Chemistry,Revised, 1989) in M⁵ include titanium, zirconium and hafnium atoms. Atitanium atom is preferable.

Examples of the atom of Group 16 of the Periodic Table of the Elementsin A² include oxygen, sulfur and selenium atoms. An oxygen atom ispreferable.

Examples of the atom of Group 14 of the Periodic Table of the Elementsrepresented by J⁴ include carbon, silicon and germanium atoms. Carbonand silicon atoms are preferable, and a carbon atom is more preferable.

Examples of the group having a cyclopentadiene-type anionic skeletonrepresented by the substituent Cp⁵ include η⁵-cyclopentadienyl,η⁵-methylcyclopentadienyl, η⁵-dimethylcyclopentadienyl,η⁵-trimethylcyclopentadienyl, η⁵-tetramethylcyclopentadienyl,η⁵-ethylcyclopentadienyl, η⁵-n-propylcyclopentadienyl,η⁵-isopropylcyclopentadienyl, η⁵-n-butylcyclopentadienyl,η⁵-sec-butylcyclopentadienyl, η⁵-tert-butylcyclopentadienyl,η⁵-n-pentylcyclopentadienyl, η⁵-neopentylcyclopentadienyl,η⁵-n-hexylcyclopentadienyl, η⁵-n-octylcyclopentadienyl,η⁵-phenylcyclopentadienyl, η⁵-naphthylcyclopentadienyl,η⁵-trimethylsilylcyclopentadienyl, η⁵-triethylsilylcyclopentadienyl,η⁵-tert-butyldimethylsilylcyclopentadienyl, η⁵-indenyl,η⁵-methylindenyl, η⁵-dimethylindenyl, η⁵-ethylindenyl,η⁵-n-propylindenyl, η⁵-isopropylindenyl, η⁵-n-butylindenyl,η⁵-sec-butylindenyl, η⁵-tert-butylindenyl, η⁵-n-pentylindenyl,η⁵-neopentylindenyl, η⁵-n-hexylindenyl, η⁵-n-octylindenyl,η⁵-n-decylindenyl, η⁵-phenylindenyl, η⁵-methylphenylindenyl,η⁵-naphthylindenyl, η⁵-trimethylsilylindenyl, η⁵-triethylsilylindenyl,η⁵-tert-butyldimethylsilylindenyl, η⁵-tetrahydroindenyl, η⁵-fluorenyl,η⁵-methylfluorenyl, η⁵-dimethylfluorenyl, η⁵-ethylfluorenyl,η⁵-diethylfluorenyl, η⁵-n-propylfluorenyl, η⁵-di-n-propylfluorenyl,η⁵-isopropylfluorenyl, η⁵-diisopropylfluorenyl, η⁵-n-butylfluorenyl,η⁵-sec-butylfluorenyl, η⁵-tert-butylfluorenyl, η⁵-di-n-butylfluorenyl,η⁵-di-sec-butylfluorenyl, η⁵-di-tert-butylfluorenyl,η⁵-n-pentylfluorenyl, η⁵-neopentylfluorenyl, η⁵-n-hexylfluorenyl,η⁵-n-octylfluorenyl, η⁵-n-decylfluorenyl, η⁵-n-dodecylfluorenyl,η⁵-phenylfluorenyl, η⁵-di-phenylfluorenyl, η⁵-methylphenylfluorenyl,η⁵-naphthylfluorenyl, η⁵-trimethylsilylfluorenyl,η⁵-bis-trimethylsilylfluorenyl, η⁵-triethylsilylfluorenyl andη⁵-tert-butyldimethylsilylfluorenyl groups. η⁵-cyclopentadienyl,η⁵-methylcyclopentadienyl, η⁵-tert-butylcyclopentadienyl,η⁵-tetramethylcyclopentadienyl, η⁵-indenyl and η⁵-fluorenyl groups, etc.are preferable.

Examples of the halogen atom in X¹⁰, X¹¹, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ includefluorine, chlorine, bromine and iodine atoms.

Examples of the alkyl group having 1 to 20 carbon atoms in X¹⁰, X¹¹,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkyl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkyl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the alkyl group having 1 to 20carbon atoms having a halogen atom as a substituent includefluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl,difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl,chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl,pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl,tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl,perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl,perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl,perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl,perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl,perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl,perbromopentadecyl and perbromoeicosyl groups.

Examples of the aryl group having 6 to 20 carbon atoms in X¹⁰, X¹¹, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include phenyl, 2-tolyl, 3-tolyl, 4-tolyl,2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryl group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the aryl group may be substituted witha halogen atom. Examples of the halogen atom include fluorine, chlorine,bromine and iodine atoms. Examples of the aryl group having 6 to 20carbon atoms having a halogen atom as a substituent includefluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl,pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.

Examples of the aralkyl group having 7 to 20 carbon atoms in X¹⁰, X¹¹,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyl group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyl group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkylgroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aralkyl group listed above with a halogen atom.

Examples of the alkoxy group having 1 to 20 carbon atoms in X¹⁰, X¹¹,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy,n-hexoxy, n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.

Moreover, the phrase “may have a halogen atom as a substituent” in the“alkoxy group which may have a halogen atom as a substituent” means thatsome or all of hydrogen atoms in the alkoxy group may be substitutedwith a halogen atom. Examples of the halogen atom include fluorine,chlorine, bromine and iodine atoms. Examples of the alkoxy group having1 to 20 carbon atoms having a halogen atom as a substituent includegroups obtained by substituting some or all of hydrogen atoms in thealkoxy group listed above with a halogen atom.

Examples of the aryloxy group having 6 to 20 carbon atoms in X¹⁰, X¹¹,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include aryloxy groups having 6 to 20carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy,4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy,2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy,3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy,2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy,3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy,2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy,pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy,n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy,n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy andanthracenoxy groups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aryloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aryloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aryloxygroup having 6 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aryloxy group listed above with a halogen atom.

Examples of the aralkyloxy group having 7 to 20 carbon atoms in X¹⁰,X¹¹, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ include benzyloxy,(2-methylphenyl)methoxy, (3-methylphenyl)methoxy,(4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy,(2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy,(2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy,(3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy,(2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy,(2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy,(3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy,(2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy,(pentamethylphenyl)methoxy, (ethylphenyl)methoxy,(n-propylphenyl)methoxy, (isopropylphenyl)methoxy,(n-butylphenyl)methoxy, (sec-butylphenyl)methoxy,(tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy,(n-octylphenyl)methoxy, (n-decylphenyl)methoxy,(n-tetradecylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxygroups.

Moreover, the phrase “may have a halogen atom as a substituent” in the“aralkyloxy group which may have a halogen atom as a substituent” meansthat some or all of hydrogen atoms in the aralkyloxy group may besubstituted with a halogen atom. Examples of the halogen atom includefluorine, chlorine, bromine and iodine atoms. Examples of the aralkyloxygroup having 7 to 20 carbon atoms having a halogen atom as a substituentinclude groups obtained by substituting some or all of hydrogen atoms inthe aralkyloxy group listed above with a halogen atom.

In the substituted silyl group represented by —Si(R¹²)₃, wherein thethree R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, in X¹⁰,X¹¹, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹, the R¹² groups are eachindependently a hydrogen atom; a hydrocarbyl group such as an alkylgroup having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl,cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an arylgroup (e.g., a phenyl group); or a halogenated hydrocarbyl groupobtained by substituting some or all hydrogen atoms in the hydrocarbylgroup by a halogen atom, and the total number of the carbon atoms in thethree R¹² groups is in the range of 1 to 20. The total number of thecarbon atoms in these three R¹² groups is preferably in the range of 3to 18. Specific examples of the substituted silyl group include:monosubstituted silyl groups having one hydrocarbyl or hydrocarbylhalide group, such as methylsilyl, ethylsilyl and phenylsilyl groups,and groups obtained by substituting some or all hydrogen atoms in thehydrocarbyl groups of these groups by a halogen atom; disubstitutedsilyl groups having two hydrocarbyl and/or halogenated hydrocarbylgroups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups,and groups obtained by substituting some or all hydrogen atoms in thehydrocarbyl groups of these groups by a halogen atom; and trisubstitutedsilyl groups having three hydrocarbyl and/or halogenated hydrocarbylgroups, such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl,triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl,tri-tert-butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl,tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl andtriphenylsilyl groups, and groups obtained by substituting some or allhydrogen atoms in the hydrocarbyl groups of these groups by a halogenatom. Of them, trisubstituted silyl groups are preferable, andtrimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, andgroups obtained by substituting some or all of hydrogen atoms in thesegroups with a halogen atom are more preferable.

In the disubstituted amino group represented by —N(R¹³)₂, wherein thetwo R¹³ groups each independently represent a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the two R¹³ groups is 2 to 20, in X¹⁰, X¹¹, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸and R¹⁹, the R¹³ moieties each independently represent a hydrocarbylgroup or a halogenated hydrocarbyl group, and the total number of thecarbon atoms in two R¹³ groups is in the range of 2 to 20, morepreferably in the range of 2 to 10. The hydrocarbyl group and thehalogenated hydrocarbyl group are the same as those described as ahydrocarbyl group and a halogenated hydrocarbyl group for thesubstituted silyl group. Moreover, these two R¹³ groups may be bonded toeach other to form a ring together with the nitrogen atom to which thetwo R¹³ groups are bonded. Examples of such a disubstituted amino groupinclude dimethylamino, diethylamino, di-n-propylamino, diisopropylamino,di-n-butylamino, di-sec-butylamino, di-tert-butylamino,di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino,di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino,bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl,carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groupsobtained by substituting some or all hydrogen atoms in these groups by ahalogen atom. Of them, dimethylamino, diethylamino, pyrrolidinyl andpiperidinyl groups, and groups obtained by substituting some or all ofhydrogen atoms in these groups with a halogen atom are preferable.

Of R¹⁴, R¹⁵, R¹⁶ and R¹⁷, two groups bonded to two adjacent carbon atomsmay be bonded to each other to form a ring together with the two carbonatoms to which the two groups are bonded, and R¹⁸ and R¹⁹ may be bondedto each other to form a ring together with J⁴ to which R¹⁸ and R¹⁹ arebonded. Examples of the ring include saturated or unsaturatedhydrocarbyl rings and can specifically include cyclopropane,cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene,cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane,cyclooctene, benzene, naphthalene and anthracene rings. These rings maybe substituted by a hydrocarbyl group having 1 to 20 carbon atoms or thelike, or may contain a silicon atom. Examples of the ring containing asilicon atom include silacyclopropane, silacyclobutane, silacyclopentaneand silacyclohexane rings.

The substituents X¹⁰ and X¹¹ are preferably a halogen atom, an alkylgroup having 1 to 20 carbon atoms which may have a halogen atom as asubstituent, or an aralkyl group having 7 to 20 carbon atoms which mayhave a halogen atom as a substituent, more preferably a halogen atom.

R¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which mayhave a halogen atom as a substituent, an aryl group having 6 to 20carbon atoms which may have a halogen atom as a substituent, an aralkylgroup having 7 to 20 carbon atoms which may have a halogen atom as asubstituent, or a substituted silyl group represented by —Si(R¹²)₃,wherein the three R¹² groups each independently represent a hydrogenatom, a hydrocarbyl group or a halogenated hydrocarbyl group, and thetotal number of the carbon atoms in the three R¹² groups is 1 to 20.Specific examples thereof include methyl, ethyl, isopropyl, tert-butyl,amyl, phenyl, benzyl, trimethylsilyl, tert-butyldimethylsilyl andtriphenylsilyl groups. More preferable examples thereof includetert-butyl, trimethylsilyl, tert-butyldimethylsilyl and triphenylsilylgroups.

The transition metal complex represented by the general formula (5) canbe produced, for example, by a method described in JP 9-87313 A.

Examples of the complex represented by the general formula (5) include:transition metal complexes represented by the general formula (5)wherein J⁴ is a carbon atom, such asmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

isopropylidene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,isopropylidene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,

diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, and compounds obtained by replacing titanium in thesecompounds with zirconium or hafnium; replacing chloride therein withbromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide,isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide;replacing (cyclopentadienyl) therein with (dimethylcyclopentadienyl),(trimethylcyclopentadienyl), (n-butylcyclopentadienyl),(tert-butyldimethylsilylcyclopentadienyl) or (indenyl); replacing3,5-dimethyl-2-phenoxy therein with 2-phenoxy, 3-methyl-2-phenoxy,3,5-di-tert-butyl-2-phenoxy, 3-phenyl-5-methyl-2-phenoxy,3-tert-butyldimethylsilyl-2-phenoxy or 3-trimethylsilyl-2-phenoxy; orreplacing methylene therein with diethylmethylene; and

transition metal complexes represented by the general formula (5)wherein J⁴ is an atom of Group 14 of the Periodic Table of the Elementsother than a carbon atom, such asdimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride,dimethylsilylene(cyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titanium dichloride,dimethylsilylene(methylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(n-butylcyclopentadienyl)(2-phenoxy)titanium dichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(tert-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(indenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,

dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(fluorenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(1-naphthoxy-2-yl)titaniumdichloride, and compounds obtained by replacing (cyclopentadienyl) inthese compounds with (dimethylcyclopentadienyl),(trimethylcyclopentadienyl), (ethylcyclopentadienyl),(n-propylcyclopentadienyl), (isopropylcyclopentadienyl),(sec-butylcyclopentadienyl), (isobutylcyclopentadienyl),(tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl),(methylindenyl) or (phenylindenyl); replacing 2-phenoxy therein with3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or3-tert-butyldimethylsilyl-2-phenoxy, changing dimethylsilylene thereininto diethylsilylene, diphenylsilylene or dimethoxysilylene, changingtitanium therein into zirconium or hafnium; or replacing chloridetherein with bromide, iodide, hydride, methyl, phenyl, benzyl,methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide,dimethylamide or diethylamide.

An unbridged bismetallocene complex can also be used as the catalyticcomponent for olefin polymerization, and examples thereof includebis(cyclopentadienyl)zirconium dichloride,bis(methylcyclopentadienyl)zirconium dichloride,bis(n-butylcyclopentadienyl)zirconium dichloride,bis(t-butylcyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride,bis(indenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride,(cyclopentadienyl)(methylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride,

(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,(cyclopentadienyl)(indenyl)zirconium dichloride,(cyclopentadienyl)(fluorenyl)zirconium dichloride, and compoundsobtained by replacing zirconium in these compounds with titanium orhafnium; replacing cyclopentadienyl therein with methylcyclopentadienyl,n-butylcyclopentadienyl, t-butylcyclopentadienyl,tetramethylcyclopentadienyl, indenyl or fluorenyl; or replacing chloridetherein with bromide, iodide, hydride, methyl, phenyl, benzyl,methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide,dimethylamide or diethylamide.

A transition metal complex of Group 4 of the Periodic Table of theElements having an amide-pyridyl-aryl ligand can also be used as thecatalytic component for olefin polymerization, and examples thereofinclude 2-(N-phenylamido-phenylmethyl)-6-(2-η-phenyl)-pyridyl hafniumdimethyl, 2-(N-phenylamido-phenylmethyl)-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-phenylmethyl]-6-(2-η⁵-phenyl)-pyridylhafnium dimethyl,2-[(N-phenylamido)-o-isopropylphenylmethyl]-6-(2-η⁵-phenyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-phenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[(N-phenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-phenyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-o-cyclohexylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-o-methylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl,2-[N-(2,6-diisopropylphenylamido)-o-phenylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium dimethyl, and compounds obtained by replacing hafnium in thesecompounds with titanium or zirconium; or replacing dimethyl therein intobistrimethylsilylmethyl. These compounds can be produced, for example,by a method described in US2004/0220050A1.

<Olefin Polymerization Catalyst>

The olefin polymerization catalyst used in the present invention is acatalyst obtainable by bringing a catalytic component for olefinpolymerization comprising the transition metal complex represented bythe general formula (2), a catalytic component for trimerizationcomprising the transition metal complex represented by the generalformula (1) and the activating co-catalytic component into contact witheach other.

In the amount of each catalytic component used, a molar ratio betweenthe catalytic component for trimerization and the catalytic componentfor olefin polymerization (catalytic component fortrimerization/catalytic component for olefin polymerization) is usually0.0001 to 100, preferably 0.001 to 1, more preferably 0.01 to 0.5, evenmore preferably 0.05 to 0.15.

In the amount of each catalytic component used, a molar ratio betweenthe compound (A) (in terms of the aluminum atom) and the transitionmetal complexes used as catalytic components (total of the catalyticcomponent for trimerization and the catalytic component for olefinpolymerization) (compound (A) (in terms of the aluminum atom)/transitionmetal complexes) is usually 0.01 to 10000, preferably 5 to 2000.Moreover, a molar ratio between the compound (B) and the transitionmetal complexes used as catalytic components (total of the catalyticcomponent for trimerization and the catalytic component for olefinpolymerization) (compound (B)/transition metal complexes) is usually0.01 to 100, preferably 0.5 to 10.

Moreover, a ratio between the mole of aluminum atoms in the compound (A)and the mole of titanium atoms in the solid catalytic component (mole ofaluminum atoms in the compound (A)/mole of titanium atoms in the solidcatalytic component) is usually 1 to 10000, preferably 1 to 2000, morepreferably 2 to 600.

When each catalytic component is used in a solution state, theconcentration of the transition metal complex used as a catalyticcomponent is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.The concentration of the compound (A) is usually 0.01 to 500 mmol/L,preferably 0.1 to 100 mmol/L, in terms of the aluminum atom. Theconcentration of the compound (B) is usually 0.0001 to 5 mmol/L,preferably 0.001 to 1 mmol/L.

A catalytic component for olefin polymerization comprising thetransition metal complex represented by the general formula (2) and theactivating co-catalytic component may be supported on a carrier for use.A porous substance is preferably used as a carrier. More preferably aninorganic substance or an organic polymer, even more preferably aninorganic substance, is used. The carrier will be described later.

The method for bringing each catalytic component into contact with eachother is not particularly limited. The catalytic component for olefinpolymerization, the catalytic component for trimerization and theactivating co-catalytic component may be brought into contact with eachother in advance to prepare a polymerization catalyst, which is thensupplied to a polymerization reactor. Alternatively, these catalyticcomponents may be supplied to a polymerization reactor in any order andsubjected to contact treatment in the polymerization reactor. Thecatalytic component for olefin polymerization brought into contact withthe catalytic component for trimerization in advance (including asimultaneous product of the catalytic component for olefinpolymerization and the catalytic component for trimerization) may alsobe supplied to a polymerization reactor; the catalytic component forolefin polymerization brought into contact with the activatingco-catalytic component in advance may be supplied thereto; or thecatalytic component for trimerization brought into contact with theactivating co-catalytic component in advance may be supplied thereto.

(Carrier)

Examples of the inorganic substance used as a carrier include inorganicoxides and magnesium compounds. Clay, clay mineral, or the like may alsobe used. They may be mixed for use.

Specific examples of the inorganic oxides used as a carrier can includeSiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂ and mixturesthereof, for example, SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅,SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgO. Among these inorganic oxides, SiO₂ andAl₂O₃ are preferable, and SiO₂ is more preferable. These inorganicoxides may contain a small amount of a carbonate, sulfate, nitrate oroxide component such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃,BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O, and Li₂O.

Moreover, the inorganic oxides usually have a hydroxy group formed onthe surface. Modified inorganic oxides obtained by substituting activehydrogen in the surface hydroxy group by various substituents may beused as the inorganic oxides, and a preferable substituent is a silylgroup. Specific examples of the modified inorganic oxides includeinorganic oxides treated by contact with trialkylchlorosilane such astrimethylchlorosilane and tert-butyldimethylchlorosilane,triarylchlorosilane such as triphenylchlorosilane, dialkyldichlorosilanesuch as dimethyldichlorosilane, diaryldichlorosilane such asdiphenyldichlorosilane, alkyltrichlorosilane such asmethyltrichlorosilane, aryltrichlorosilane such asphenyltrichlorosilane, trialkylalkoxysilane such astrimethylmethoxysilane, triarylalkoxysilane such astriphenylmethoxysilane, dialkyldialkoxysilane such asdimethyldimethoxysilane, diaryldialkoxysilane such asdiphenyldimethoxysilane, alkyltrialkoxysilane such asmethyltrimethoxysilane, aryltrialkoxysilane such asphenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane,alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane,tetrachlorosilane, or the like.

Examples of the magnesium compounds used as a carrier can include:magnesium halide such as magnesium chloride, magnesium bromide,magnesium iodide and magnesium fluoride; alkoxy magnesium halide such asmethoxy magnesium chloride, ethoxy magnesium chloride, isopropoxymagnesium chloride, butoxy magnesium chloride and octoxy magnesiumchloride; aryloxy magnesium halide such as phenoxy magnesium chlorideand methylphenoxy magnesium chloride; alkoxymagnesium such asethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesiumand 2-ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesiumand dimethylphenoxymagnesium; and carboxylate of magnesium such asmagnesium laurate and magnesium stearate. Among them, magnesium halideor alkoxymagnesium is preferable, and magnesium chloride orbutoxymagnesium is more preferable.

Examples of the clay or clay mineral used as a carrier include kaolin,bentonite, kibushi clay, gairome clay, allophane, hisingerite,pyrophyllite, talc, micas isinglass, montmorillonites, vermiculite,chlorites, palygorskite, kaolinite, nacrite, dickite and halloysites.Among them, smectite, montmorillonite, hectorite, Laponite or saponiteis preferable, and montmorillonite or hectorite is more preferable.

The inorganic substance used as a carrier is preferably inorganic oxide.

These inorganic substances used as a carrier are preferably dried, foruse, by heat treatment. The temperature of the heat treatment is usually100 to 1500° C., preferably 100 to 1000° C., more preferably 200 to 800°C. The time of the heat treatment is not particularly limited and ispreferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.Examples of the method for the heat treatment include, but not limitedto, a method in which after heating, for example, dried inert gas (e.g.,nitrogen or argon) is circulated at a constant flow rate for a few hoursor longer, and a method in which the pressure is reduced for a fewhours.

The average particle size of the carrier comprising the inorganicsubstance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, evenmore preferably 10 to 100 μm. The pore volume of the carrier comprisingthe inorganic substance is preferably 0.1 ml/g or larger, morepreferably 0.3 to 10 ml/g. The specific surface of the carriercomprising the inorganic substance is preferably 10 to 1000 m²/g, morepreferably 100 to 500 m²/g.

The organic polymer used as a carrier is not particularly limited, andtwo or more organic polymers may be used as a mixture. A polymer havinga group having active hydrogen and/or a non-proton-donating Lewis-basicgroup is preferable.

The group having active hydrogen is not particularly limited as long asit has active hydrogen. Specific examples thereof include primary amino,secondary amino, imino, amide, hydrazide, amidino, hydroxy, hydroperoxy,carboxyl, formyl, carbamoyl, sulfonic acid, sulfinic acid, sulfenicacid, thiol, thioformyl, pyrrolyl, imidazolyl, piperidyl, indazolyl andcarbazolyl groups. A primary amino, secondary amino, imino, amide,imide, hydroxy, formyl, carboxyl, sulfonic acid or thiol group ispreferable. A primary amino, secondary amino, amide or hydroxy group isparticularly preferable. These groups may be substituted by a halogenatom or a hydrocarbyl group having 1 to 20 carbon atoms.

The non-proton-donating Lewis-basic group is not particularly limited aslong as it is a group having a Lewis base moiety free from an activehydrogen atom. Specific examples thereof include pyridyl, N-substitutedimidazolyl, N-substituted indazolyl, nitrile, azide, N-substitutedimino, N,N-substituted amino, N,N-substituted aminooxy,N,N,N-substituted hydrazino, nitroso, nitro, nitrooxy, furyl, carbonyl,thiocarbonyl, alkoxy, alkyloxycarbonyl, N,N-substituted carbamoyl,thioalkoxy, substituted sulfinyl, substituted sulfonyl and substitutedsulfonic acid groups. Heterocyclic groups are preferable, and aromaticheterocyclic groups having oxygen and/or nitrogen atoms in the ring aremore preferable. A pyridyl, N-substituted imidazolyl or N-substitutedindazolyl group is particularly preferable, with a pyridyl group mostpreferred. These groups may be substituted by a halogen atom or ahydrocarbyl group having 1 to 20 carbon atoms.

The amount of the group having active hydrogen and thenon-proton-donating Lewis-basic group in the polymer is preferably 0.01to 50 mmol/g, more preferably 0.1 to 20 mmol/g, in terms of the molaramount of the group per unit gram of the polymer.

The polymer having such group(s) can be obtained, for example, byhomopolymerizing monomers having the group having active hydrogen and/orthe non-proton-donating Lewis-basic group and one or more polymerizableunsaturated groups or by copolymerizing this monomer with additionalmonomer(s) having one or more polymerizable unsaturated groups.Moreover, a crosslinking polymerizable monomer having two or morepolymerizable unsaturated groups is preferably used as at least one ofthe additional monomers.

Examples of such monomers having the group having active hydrogen and/orthe non-proton-donating Lewis-basic group and one or more polymerizableunsaturated groups can include monomers having the group having activehydrogen and one or more polymerizable unsaturated groups, and monomershaving the group having a Lewis base moiety free from an active hydrogenatom and one or more polymerizable unsaturated groups. Examples of suchpolymerizable unsaturated groups include: alkenyl groups such as vinyland allyl; and alkynyl groups such as an ethyne group.

Examples of the monomers having the group having active hydrogen and oneor more polymerizable unsaturated groups can include vinylgroup-containing primary amine, vinyl group-containing secondary amine,vinyl group-containing amide compounds and vinyl group-containinghydroxy compounds. Specific examples thereof include N-(1-ethenyl)amine,N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine,N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide,N-methyl-(1-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol,2-propen-1-ol and 3-buten-1-ol.

Specific examples of the monomers having the non-proton-donatingLewis-basic group and one or more polymerizable unsaturated groups caninclude vinylpyridine, vinyl (N-substituted) imidazole and vinyl(N-substituted) indazole.

Examples of the additional monomers having one or more polymerizableunsaturated groups include olefin and aromatic vinyl compounds andspecifically include ethylene, propylene, 1-butene, 1-hexene,4-methyl-1-pentene and styrene. Ethylene or styrene is preferable. Thesemonomers may be used in combination of two or more thereof. Moreover,specific examples of the crosslinking polymerizable monomer having twoor more polymerizable unsaturated groups include divinylbenzene.

The average particle size of the carrier comprising the organic polymeris preferably 5 to 1000 μm, more preferably 10 to 500 μm. The porevolume of the carrier comprising the organic polymer is preferably 0.1ml/g or larger, more preferably 0.3 to 10 ml/g. The specific surface ofthe carrier comprising the organic polymer is preferably 10 to 1000m²/g, more preferably 50 to 500 m²/g.

These organic polymers used as a carrier are preferably dried, for use,by heat treatment. The temperature of the heat treatment is usually 30to 400° C., preferably 50 to 200° C., more preferably 70 to 150° C. Thetime of the heat treatment is not particularly limited and is preferably10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples ofthe method for the heat treatment include, but not limited to, a methodin which after heating, for example, dried inert gas (e.g., nitrogen orargon) is circulated at a constant flow rate for a few hours or longer,and a method in which the pressure is reduced for a few hours.

The geometric standard deviation of the particle size of the carrierbased on the volume is preferably 2.5 or lower, more preferably 2.0 orlower, even more preferably 1.7 or lower.

<Polymerization>

The present invention relates to a process for producing an ethylenicpolymer, comprising polymerizing ethylene in the presence of the olefinpolymerization catalyst. The polymerization may be performed bysupplying only ethylene as a raw material monomer or by supplying anethylene-copolymerizable monomer and ethylene.

Examples of the ethylene-copolymerizable monomer include: olefin having3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-penteneand 4-methyl-1-hexene; cyclic olefin such as norbornene; alkenylaromatic hydrocarbyl such as styrene; unsaturated carboxylic acid suchas acrylic acid and methacrylic acid; unsaturated carboxylic ester suchas methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylateand ethyl methacrylate; and vinyl ester compounds such as vinyl acetate.These monomers may be used alone or in combination of two or morethereof.

The polymerization process is not particularly limited and can be, forexample, solvent polymerization using aliphatic hydrocarbyl (butane,pentane, hexane, heptane, octane, etc.), aromatic hydrocarbyl (benzene,toluene, etc.) or hydrocarbyl halide (methylene dichloride, etc.) as asolvent, slurry polymerization, gas-phase polymerization performed inmonomers in a gas state, or the like. Moreover, both continuouspolymerization and batch polymerization may be used.

The present invention can produce a polymer having a butyl branch evenby polymerization using hexene supplied in small amounts as a rawmaterial monomer or by polymerization using only ethylene supplied as araw material monomer. Therefore, polymerization conditions that make theadvantages of the present invention more significant involve an ethylenemolar fraction (the total amount of ethylene and 1-hexene in thepolymerization system is defined as 100 mol %) of preferably 90 mol % orlarger, more preferably 95 mol % or larger, even more preferably,substantially 100 mol %, in the polymerization system, when thepolymerization form is slurry polymerization. Moreover, when thepolymerization form is gas-phase polymerization, the ethylene molarfraction (the total amount of ethylene and 1-hexene in thepolymerization system is defined as 100 mol %) is preferably 97 mol % orlarger, more preferably 98 mol % or larger, even more preferably,substantially 100 mol %, in the polymerization system.

For the solution polymerization and the slurry polymerization, theconcentration of the olefin polymerization catalyst in thepolymerization solution is usually 0.0001 to 5 mmol/L in terms of themole of the transition metal complexes used as catalytic components(total of the catalytic component for trimerization and the catalyticcomponent for olefin polymerization). The concentration of the olefinpolymerization catalyst is preferably 2 mmol/L or lower, more preferably1 mmol/L or lower, for enhancing the economy. Moreover, theconcentration of the olefin polymerization catalyst is preferably 0.001mmol/L or higher, more preferably 0.01 mmol/L or higher, even morepreferably 0.1 mmol/L or higher, particularly preferably 0.5 mmol/L orhigher, for more increasing the number of butyl branches.

The polymerization pressure is preferably normal pressure to 5 MPa. Thepolymerization time is generally determined appropriately according tothe type of the polymer of interest and a reaction apparatus and can bein the range of 1 minute to 20 hours. Moreover, a chain transfer agentsuch as hydrogen can also be added for adjusting the molecular weight ofthe ethylenic polymer.

The polymerization temperature can be in the range of 0° C. to 220° C.The polymerization temperature is preferably 20° C. or higher, morepreferably 40° C. or higher, even more preferably 50° C. or higher, mostpreferably 70° C. or higher, to improve the economic efficiency.Moreover, the polymerization temperature is preferably 130° C. or lower,more preferably 100° C. or lower, for more increasing the number ofbutyl branches.

<Polymer>

Examples of the ethylenic polymer obtained by the production process ofthe present invention include ethylene-1-hexene,ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene,ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene,ethylene-1-hexene-1-butene-1-octene,ethylene-1-hexene-1-butene-4-methyl-1-pentene,ethylene-1-hexene-styrene, ethylene-1-hexene-norbornene,ethylene-1-hexene-propylene-styrene andethylene-1-hexene-propylene-norbornene copolymers.

The ethylenic polymer is preferably an ethylene-1-hexene,ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene,ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene,ethylene-1-hexene-styrene or ethylene-1-hexene-norbornene copolymer,more preferably an ethylene-1-hexene or ethylene-1-hexene-1-butenecopolymer.

The number of butyl branches per 1000 carbon atoms in the ethylenicpolymer is preferably 1 or more, more preferably 3 or more, even morepreferably 5 or more, particularly preferably 10 or more, from theviewpoint of enhancing the mechanical strength of the ethylenic polymer.Moreover, the number of butyl branches is preferably 40 or less, morepreferably 30 or less, even more preferably 25 or less, from theviewpoint of enhancing the stiffness of the ethylenic polymer. Thenumber of butyl branches can be determined by a method such as carbonnuclear magnetic resonance (¹³C-NMR) or IR.

The melting point of the ethylenic polymer is preferably lower than 130°C. from the viewpoint of enhancing the mechanical strength of theethylenic polymer. The melting point can be determined using adifferential scanning calorimeter.

The number of butyl branches per 1000 carbon atoms in the ethylenicpolymer can be increased by increasing a molar ratio between thecatalytic component for trimerization and the catalytic component forolefin polymerization (catalytic component for trimerization/catalyticcomponent for olefin polymerization) used in the preparation of thepolymerization catalyst or by lowering the polymerization temperature.

The molecular weight distribution (Mw/Mn) of the ethylenic polymer ispreferably 1.5 or higher for enhancing the processability of thepolymer. Moreover, Mw/Mn is preferably 20 or lower for enhancing themechanical strength of the polymer. The molecular weight distribution(Mw/Mn) is a value (Mw/Mn) obtained by determining the weight-averagemolecular weight (Mw) and the number-average molecular weight (Mn) bygel permeation chromatography against polystyrene standards and dividingMw by Mn.

The ethylenic polymer is molded, for use, into various moldings (e.g.,films, sheets and containers (bottles, trays, etc.)) by a molding methodknown in the art, for example: extrusion methods such as inflation filmmolding and T-die film molding; hollow molding, injection molding;compression molding; and cross-linked foaming molding.

The ethylenic polymer may be blended with a resin known in the art andthen molded. Moreover, the moldings may be monolayer molding containingthe ethylenic polymer or may be multilayer molding containing theethylenic polymer.

Examples of the moldings include films for food package, containers forfood package, packaging materials for pharmaceuticals,surface-protective films, packaging materials for electronic parts usedin package for semiconductor products or the like, cross-linked foamedmoldings, injection foamed moldings, hollow moldings, blow bottles andsqueeze bottles.

EXAMPLES

The present invention will be described by way of Examples andComparative Examples below.

<Production of Transition Metal Complex>

Physical properties were measured according to the following methods.

(1) Proton Nuclear Magnetic Resonance Spectrum (¹H-NMR)

Apparatus: EX270 manufactured by JEOL Ltd.Sample cell: Tube (5 mm in diameter)Measurement solvent: CDCl₃ or CD₂Cl₂Sample concentration: 10 mg/0.5 mL (CDCl₃ or CD₂Cl₂)Measurement temperature: Room temperature (about 25° C.)Measurement parameter: Probe (5 mm in diameter), EXMOD NON, OBNUC ¹H,accumulated number 16 times or moreRepeat time: ACQTM 6 seconds, PD 1 secondInternal standard: CDCl₃ (7.26 ppm) or CD₂Cl₂ (5.32 ppm)

(2) Carbon Nuclear Magnetic Resonance Spectrum (¹³C-NMR)

Apparatus: EX270 manufactured by JEOL Ltd.Sample cell: Tube (5 mm in diameter)Measurement solvent: CDCl₃ or CD₂Cl₂Sample concentration: 30 mg/0.5 mL (CDCl₃ or CD₂Cl₂)Measurement temperature: Room temperature (about 25° C.)Measurement parameter: Probe (5 mm in diameter), EXMOD BCM, OBNUC ¹³C,accumulated number 256 times or moreRepeat time: ACQTM 1.79 seconds, PD 1.21 secondsInternal standard: CDCl₃ (77.0 ppm) or CD₂Cl₂ (53.8 ppm)

(3) Mass Spectrum

[Electron Ionization Mass Spectrometry (EI-MS)]

Apparatus: JMS-T100GC manufactured by JEOL Ltd.Ionization voltage: 70 eVIon source temperature: 230° C.Acceleration voltage: 7 kV

MASS RANGE: m/z 35-800 Example 1 Synthesis of[1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 1”) Synthesis of1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.80 g, 33.47 mmol as pure sodium hydride) andtetrahydrofuran (38 mL) were mixed. This mixture was heated to 50° C.and aniline (0.21 g, 2.23 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.00 g, 24.55 mmol) dissolved in tetrahydrofuran (10 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then the resultantmixture was cooled to 0° C. To this solution, a solution ofchloro(n-butyl)methylphenylsilane (4.75 g, 22.32 mmol) dissolved intoluene (10 mL) was added dropwise and stirred at 35° C. for 2 hours.The resultant mixture was added dropwise at 0° C. to a mixed solution ofa 10% sodium hydrogen carbonate (24 mL) and a 10% sodium carbonate (24mL). Toluene (24 mL) was added to separate an organic phase, and theorganic phase was washed with water (40 mL) and further washed withsaturated brine (20 mL). After the organic phase was dried over sodiumsulfate and filtrated, the solvent was removed under reduced pressure toobtain 1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene(5.16 g, yield 77.4%).

¹H-NMR (CDCl₃, δppm): 0.13 (s, 3H), 0.66-0.90 (m, 2H), 0.84 (t, J=7.0Hz, 3H), 1.15-1.35 (m, 4H), 1.67 (s, 3H), 1.71 (s, 3H), 1.73 (s, 3H),1.80 (s, 3H), 3.10 (s, 1H), 7.29-7.36 (m, 3H), 7.41-7.47 (m, 2H)

Mass Spectrum (EI-MS, m/z): 298 (M⁺)

Synthesis of Complex 1

Under a nitrogen atmosphere, to a toluene solution (23 mL) of1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (2.30 g,7.70 mmol) and triethylamine (1.95 g, 19.25 mmol), a 1.55 M hexanesolution of n-butyllithium (6.21 mL, 9.63 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at 35° C. for 2.5 hours. The resultant mixturewas cooled to −78° C. and a solution of titanium tetrachloride (2.19 g,11.55 mmol) dissolved in toluene (12 mL) was added dropwise at the sametemperature. The mixture was warmed and the internal temperature was setto 60° C. Thereafter, the mixture was stirred at the same temperaturefor 2 hours. After completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and a precipitatedwhite solid was removed by filtration. The resultant filtrate was cooledto −20° C. The resultant solid was filtrated and washed with a smallamount of pentane, and then dried under reduced pressure to obtaincomplex 1 (0.25 g, yield 7.2%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.76 (s, 3H), 0.87 (t, J=7.0 Hz, 3H), 1.23-1.42(m, 6H), 2.27 (s, 3H), 2.28 (s, 3H), 2.36 (s, 3H), 2.46 (s, 3H),7.30-7.42 (m, 3H), 7.43-7.52 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −2.61, 13.69, 14.13, 14.32, 14.90, 17.71, 17.81,25.86, 26.51, 128.01, 129.53, 134.45, 136.25, 139.44, 141.96, 142.47,144.63, 144.92

Mass Spectrum (EI-MS, m/z): 393 (M⁺-Bu)

Example 2 Synthesis of[1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 2”) Synthesis of1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.54 g, 22.32 mmol as pure sodium hydride) andtetrahydrofuran (28 mL) were mixed. This mixture was heated to 50° C.and aniline (0.14 g, 1.49 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.00 g, 24.55 mmol) dissolved in tetrahydrofuran (7 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then was cooled to 20°C. To this solution, a solution of chloromethyldiphenylsilane (3.46 g,14.88 mmol) dissolved in toluene (7 mL) was added dropwise and stirredat 35° C. overnight. The resultant mixture was added dropwise at 0° C.to a mixed solution of a 10% sodium hydrogen carbonate (17 mL) and a 10%sodium carbonate (17 mL). Toluene (17 mL) was added to separate anorganic phase, and the organic phase was dried over sodium sulfate andfiltrated. The solvent was concentrated under reduced pressure to obtain1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (4.10 g, yield86.5%).

Synthesis of Complex 2

Under a nitrogen atmosphere, to a toluene solution (38 mL) of1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.90 g, 5.97mmol) and triethylamine (3.02 g, 29.86 mmol), a 1.55 M hexane solutionof n-butyllithium (4.62 mL, 7.17 mmol) was added dropwise at −78° C.After the mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 3 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (1.25 g, 6.57 mmol)dissolved in toluene (7 mL) was added dropwise at the same temperature.The mixture was warmed and the internal temperature was set to 35° C.Thereafter, the mixture was stirred at the same temperature for onehour. After completion of the reaction, the solvent was removed underreduced pressure. The residue, to which heptane was added, was filtratedto remove insoluble materials. The solvent was removed under reducedpressure. Pentane was added, the resultant solid was filtrated andwashed with a small amount of pentane and then dried under reducedpressure to obtain complex 2 (0.94 g, yield 33.2%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 2.12 (s, 6H), 2.34 (s, 6H), 7.31-7.50 (m, 10H)

¹³C-NMR (CDCl₃, δppm): −1.04, 14.27, 17.69, 128.11, 129.91, 135.08,135.38, 137.44, 142.33, 145.22

Mass Spectrum (EI-MS, m/z): 470 (M⁺)

Example 3 Synthesis of[1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 3”) Synthesis of1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (1.21 g, 50.32 mmol as pure sodium hydride) andtetrahydrofuran (57 mL) were mixed. This mixture was heated to 50° C.and aniline (0.31 g, 3.35 mmol) was added and stirred at 50° C. for 1.5hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(4.51 g, 36.90 mmol) dissolved in tetrahydrofuran (14 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.To this solution, a solution of chlorocyclohexylmethylphenylsilane (8.01g, 33.55 mmol) dissolved in toluene (14 mL) was added dropwise andstirred at room temperature for 3 hours. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (72 ml).Toluene (100 mL) was added to separate an organic phase, and the organicphase was washed with water (100 mL) twice and further washed withsaturated saline (50 mL). After the organic phase was dried over sodiumsulfate and filtrated, the solvent was removed under reduced pressure.Purification was performed by silica gel column chromatography to obtain1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (6.57g, yield 60.3%).

¹H-NMR (CDCl₃, δppm): 0.03 (s, 3H), 1.05-1.37 (m, 6H), 1.58-1.84 (m,14H), 1.94 (s, 3H), 3.23 (s, 1H), 7.23-7.34 (m, 3H), 7.36-7.42 (m, 2H)

Mass Spectrum (EI-MS, m/z): 324 (M⁺)

Synthesis of Complex 3

Under a nitrogen atmosphere, to a toluene solution (49 mL) of1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (2.27g, 7.00 mmol) and triethylamine (3.54 g, 35.00 mmol), a 1.65 M hexanesolution of n-butyllithium (5.09 mL, 8.40 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 2 hours. The resultantmixture was cooled to −78° C. and a solution of titanium tetrachloride(1.46 g, 7.70 mmol) dissolved in toluene (8 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 2 hours.After completion of the reaction, the solvent was removed under reducedpressure. Thereafter, the residue, to which heptane was added, wasfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. Pentane was added and the resultant solid wasfiltrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 3 (1.19 g, yield 35.6%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 0.80 (s, 3H), 1.04-1.50 (m, 6H), 1.56-1.84 (m,5H), 2.15 (s, 3H), 2.24 (s, 3H), 2.41 (s, 3H), 2.61 (s, 3H), 7.30-7.43(m, 3H), 7.49-7.60 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −3.47, 14.15, 14.50, 17.73, 17.79, 24.90, 26.73,27.73, 28.06, 28.13, 28.24, 127.83, 129.54, 134.90, 135.31, 139.69,141.89, 142.81, 144.45, 144.71

Mass Spectrum (EI-MS, m/z): 394 (M⁺-Cy) (Cy: cyclohexyl)

Example 4 Synthesis of[1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 4”) Synthesis of1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.82 g, 34.09 mmol as pure sodium hydride) andtetrahydrofuran (39 mL) were mixed. This mixture was heated to 50° C.and aniline (0.21 g, 2.27 mmol) was added and stirred at 50° C. for 2.5hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.06 g, 25.00 mmol) dissolved in tetrahydrofuran (10 mL) was addeddropwise and stirred at 50° C. for 2.5 hours, and then was cooled to 0°C. To this solution, a solution of chloromethyl(n-octadecyl)phenylsilane(9.30 g, 22.73 mmol) dissolved in toluene (10 mL) was added dropwise andstirred at room temperature overnight. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (50 ml).Toluene (70 mL) was added to separate an organic phase, and the organicphase was washed with water (70 mL) twice, and further washed withsaturated brine (50 mL). After dried over sodium sulfate, the organicphase was filtrated. The solvent was removed under reduced pressure.Purification was performed by silica gel column chromatography to obtain1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene(8.65 g, yield 76.9%).

¹H-NMR (CDCl₃, δppm): 0.13 (s, 3H), 0.88 (t, J=6.9 Hz, 3H), 1.17-1.32(m, 34H), 1.67 (s, 3H), 1.71 (s, 3H), 1.73 (s, 3H), 1.79 (s, 3H), 3.10(s, 1H), 7.28-7.38 (m, 3H), 7.40-7.47 (m, 2H)

Mass Spectrum (EI-MS, m/z): 494 (M⁺)

Synthesis of Complex 4

Under a nitrogen atmosphere, to a toluene solution (49 mL) of1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene(1.98 g, 4.00 mmol) and triethylamine (2.02 g, 20.00 mmol), a 1.65 Mhexane solution of n-butyllithium (2.67 mL, 4.40 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 3 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (0.83 g, 4.40 mmol) dissolved in toluene (4 mL) was addeddropwise at the same temperature. After the mixture was gradually warmedto room temperature, stirring was performed at room temperatureovernight. After completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. The resultant residue was cooled to −78°C. and washed with pentane. Hexamethyldisiloxane was added and cooled to−20° C. The resultant solid was filtrated and washed with a small amountof hexamethyldisiloxane, and then, dried under reduced pressure toobtain complex 4 (0.30 g, yield 11.7%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.76 (s, 3H), 0.88 (t, J=6.8 Hz, 3H), 1.15-1.37(m, 34H), 2.27 (s, 3H), 2.28 (s, 3H), 2.36 (s, 3H), 2.46 (s, 3H),7.29-7.40 (m, 3H), 7.43-7.52 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −2.56, 14.15, 14.34, 15.21, 17.74, 17.84, 22.72,23.72, 29.25, 29.39, 29.56, 29.68, 29.72, 31.95, 33.56, 128.03, 129.55,134.48, 136.31, 139.46, 141.94, 142.46, 144.63, 144.92

Mass Spectrum (EI-MS, m/z): 393 (M⁻-C₁₈H₃₇)

Example 5 Synthesis of[1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 5”) Synthesis of1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.80 g, 33.47 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (30mL) were mixed. This mixture was heated to 50° C. and aniline (0.21 g,2.23 mmol) was added and stirred at 50° C. for one hour. To this, asolution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.00 g, 24.55 mmol)dissolved in tetrahydrofuran (8 mL) was added dropwise and stirred at50° C. for 2 hours, and then was cooled to 0° C. To this solution, asolution of chlorodimethylphenylsilane (3.81 g, 22.32 mmol) dissolved intoluene (8 mL) was added dropwise and stirred at 35° C. The resultantmixture was added dropwise at 0° C. to a mixed solution of a 10% sodiumhydrogen carbonate (19 mL) and a 10% sodium carbonate (19 mL). Toluene(19 mL) was added to separate an organic phase, and the organic phasewas dried over sodium sulfate and filtrated. The solvent was removedunder reduced pressure and purification was performed by silica gelcolumn chromatography to obtain1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (4.08 g, yield71.3%).

Synthesis of Complex 5

Under a nitrogen atmosphere, to a toluene solution (27 mL) of1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.36 g, 5.30mmol) and triethylamine (2.68 g, 26.50 mmol), a 1.65 M hexane solutionof n-butyllithium (3.85 mL, 6.36 mmol) was added dropwise at −78° C.After the mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 2 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (1.11 g, 5.83 mmol)dissolved in toluene (6 mL) was added dropwise at the same temperature.After the mixture was warmed, the mixture was stirred at roomtemperature for 1.5 hours. After the completion of the reaction, thesolvent was removed under reduced pressure. Thereafter, the residue, towhich heptane was added, was filtrated to remove insoluble materials.The solvent was removed under reduced pressure. Pentane was added andthe resultant solid was filtrated and washed with a small amount ofpentane, and then, dried under reduced pressure to obtain complex 5(0.11 g, yield 4.9%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.77 (s, 6H), 2.33 (s, 6H), 2.40 (s, 6H),7.31-7.47 (m, 5H)

¹³C-NMR (CDCl₃, δppm): 0.20, 14.19, 17.65, 128.08, 129.57, 133.96,137.38, 138.66, 142.17, 144.90

Mass Spectrum (EI-MS, m/z): 408 (M⁺)

Example 6 Synthesis of[1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 6”) Synthesis of1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.96 g, 40.00 mmol as pure sodium hydride) andtetrahydrofuran (43 mL) were mixed. This mixture was heated to 50° C.and aniline (0.25 g, 2.67 mmol) was added and stirred at 50° C. for 1.5hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.42 g, 28.00 mmol) dissolved in tetrahydrofuran (11 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.To this solution, a solution of chlorodimethyl(3,5-dimethylphenyl)silane(5.30 g, 26.67 mmol) dissolved in toluene (11 mL) was added dropwise andstirred at room temperature overnight. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (56 ml).Toluene (80 mL) was added to separate an organic phase, and the organicphase was washed with water (80 mL) twice, and further washed withsaturated brine (50 mL). After dried over sodium sulfate, the organicphase was filtrated. The solvent was removed under reduced pressure toobtain1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(6.60 g, yield 87.0%).

¹H-NMR (CDCl₃, δppm): 0.14 (s, 6H), 1.72 (s, 6H), 1.76 (s, 6H), 2.31 (s,6H), 3.06 (s, 1H), 6.98 (s, 1H), 7.07 (s, 2H)

Mass Spectrum (EI-MS, m/z): 284 (M⁺)

Synthesis of Complex 6

Under a nitrogen atmosphere, to a toluene solution (53 mL) of1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(1.99 g, 7.00 mmol) and triethylamine (3.54 g, 35.00 mmol), a 1.65 Mhexane solution of n-butyllithium (5.09 mL, 8.40 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 3 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (1.46 g, 7.70 mmol) dissolved in toluene (8 mL) was addeddropwise at the same temperature. After the temperature was graduallywarmed to room temperature, the mixture was stirred at room temperatureovernight. After completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and cooled to −20° C.and the resultant solid was filtrate and, washed with a small amount ofpentane, and then, dried under reduced pressure to obtain complex 6(0.49 g, yield 16.0%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.74 (s, 6H), 2.30 (s, 6H), 2.33 (s, 6H), 2.41 (s,6H), 7.02 (s, 1H), 7.06 (s, 2H)

¹³C-NMR (CDCl₃, δppm): 0.41, 14.38, 17.85, 21.53, 131.51, 131.82,137.18, 137.54, 139.47, 142.33, 145.10

Mass Spectrum (EI-MS, m/z): 436 (M⁺)

Example 7 Synthesis of[1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 7”) Synthesis of1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.68 g, 28.45 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (30mL) were mixed. This mixture was heated to 50° C. and aniline (0.18 g,1.90 mmol) was added and stirred at 50° C. for one hour. To this, asolution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.55 g, 20.87 mmol)dissolved in tetrahydrofuran (8 mL) was added dropwise and stirred at50° C. for 2 hours, and then was cooled to 0° C. To this solution, asolution of chlorodiethylphenylsilane (3.77 g, 18.97 mmol) dissolved intoluene (8 mL) was added dropwise and stirred at 35° C. The resultantmixture was added dropwise at 0° C. to a mixed solution of a 10% sodiumhydrogen carbonate (19 mL) and a 10% sodium carbonate (19 mL). Toluene(19 mL) was added to separate an organic phase, and the organic phasewas dried over sodium sulfate and filtrated. The solvent was removedunder reduced pressure and purification was performed by silica gelcolumn chromatography to obtain1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (2.90 g, yield53.7%).

¹H-NMR (CDCl₃, δppm): 0.74-0.99 (m, 10H), 1.71 (s, 6H), 1.76 (s, 6H),3.17 (s, 1H), 7.27-7.32 (m, 3H), 7.40-7.44 (m, 2H)

¹³C-NMR (CDCl₃, δppm): 2.66, 7.58, 11.10, 14.47, 52.65, 127.27, 128.69,133.05, 134.15, 135.92, 136.46

Mass Spectrum (EI-MS, m/z): 284 (M⁺)

Synthesis of Complex 7

Under a nitrogen atmosphere, to a toluene solution (30 mL) of1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.38 g, 4.85mmol) and triethylamine (2.47 g, 24.41 mmol), a 1.65 M hexane solutionof n-butyllithium (3.6 mL, 6.01 mmol) was added dropwise at −78° C.After the mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 4 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (1.03 g, 5.41 mmol)dissolved in toluene (5.4 mL) was added dropwise at the sametemperature. After the mixture was warmed to room temperature, themixture was stirred at room temperature overnight. After completion ofthe reaction, the solvent was removed under reduced pressure. Theresidue, to which heptane was added, was filtrated to remove insolublematerials. The solvent was removed under reduced pressure. Pentane wasadded and the resultant solid was filtrated and washed with a smallamount of pentane. The solid, to which toluene was added, was filtratedto remove insoluble materials. The solvent was removed under reducedpressure. Pentane was added and the resultant solid was filtrated andwashed with a small amount of pentane, and then, concentrated underreduced pressure to obtain complex 7 (0.032 g, yield 1.5%) as an orangesolid.

¹H-NMR (CDCl₃, δppm): 0.99 (t, J=7.8 Hz, 6H), 1.29-1.39 (m, 4H), 2.31(s, 6H), 2.35 (s, 6H), 7.36-7.41 (m, 3H), 7.56-7.60 (m, 2H)

¹³C-NMR (CDCl₃, δppm): 5.13, 7.71, 14.31, 17.80, 128.00, 129.63, 134.43,135.17, 139.81, 142.36, 144.61

Mass Spectrum (EI-MS, m/z): 407 (M⁺-Et)

Example 8 Synthesis of[1-(3,5-di-n-hexylphenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 8”) Synthesis of1-(3,5-di-n-hexylphenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol in termsof pure sodium hydride) dispersed in mineral oil was washed with hexaneto remove the mineral oil, and then tetrahydrofuran (23 mL) was addedthereto. This mixture was heated to 50° C. and aniline (0.13 g, 1.36mmol) was added and stirred at 50° C. for one hour. To this, a solutionof 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.83 g, 15.00 mmol)dissolved in tetrahydrofuran (6 mL) was added dropwise and stirred at50° C. for 3 hours and a half, and then was cooled to 0° C. To thissolution, a solution of chloro(3,5-di-n-hexylphenyl)dimethylsilane (4.62g, 13.64 mmol) dissolved in toluene (6 mL) was added dropwise andstirred at room temperature for 4 hours. The resultant mixture was addeddropwise at 0° C. to 10% aqueous solution of sodium carbonate (50 mL).Toluene (50 mL) was added to separate an organic phase, and the organicphase was washed twice with water (50 mL) and further washed withsaturated brine (50 mL). The organic phase was dried over sodium sulfateand then filtrated and concentrated by removing the solvent underreduced pressure. Purification was performed by silica gel columnchromatography to obtain1-(3,5-di-n-hexylphenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene(3.53 g, yield 60.9%).

¹H-NMR (CDCl₃, 6 ppm): 0.19 (s, 6H), 0.90 (t, J=6.9 Hz, 6H), 1.23-1.44(m, 12H), 1.53-1.68 (m, 4H), 1.74 (s, 6H), 1.78 (s, 6H), 2.59 (t, J=7.4Hz, 4H), 3.08 (s, 1H), 6.98 (s, 1H), 7.08 (s, 2H)

Mass Spectrum (EI-MS, m/z): 424 (M⁺)

Synthesis of Complex 8

Under a nitrogen atmosphere, to a toluene solution (44 mL) of1-(3,5-di-n-hexylphenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene(1.91 g, 4.50 mmol) and triethylamine (2.28 g, 22.50 mmol), a 1.65 Mhexane solution of n-butyllithium (3.27 mL, 5.40 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 6 hours. Theresultant mixture was cooled to −78° C. and a solution (5 mL) oftitanium tetrachloride (0.94 g, 4.95 mmol) dissolved in toluene wasadded dropwise at the same temperature. After the mixture was graduallywarmed to room temperature, the mixture was stirred at room temperatureovernight. After the reaction, the solvent was concentrated underreduced pressure, and then, heptane was added to the residue andfiltered to remove insoluble materials. The solvent was removed from thefiltrate under reduced pressure and complex 8 (0.73 g) was obtained asred oil.

¹H-NMR (CDCl₃, 6 ppm): 0.74 (s, 6H), 0.82-0.93 (m, 6H), 1.21-1.38 (m,12H), 1.48-1.67 (m, 4H), 2.32 (s, 6H), 2.38 (s, 6H), 2.49-2.61 (m, 4H),6.95 (s, 1H), 7.06 (s, 2H)

Mass Spectrum (EI-MS, m/z): (576 M⁻)

Example 9 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 9”) Synthesis of1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.54 g, 22.32 mmol as pure sodium hydride) andtetrahydrofuran (35 mL) were mixed. This mixture was heated to 50° C.and aniline (0.14 g, 1.49 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(2.00 g, 16.37 mmol) dissolved in tetrahydrofuran (9 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then was cooled to 20°C. To this solution, a solution of chlorotriphenylsilane (4.39 g, 14.88mmol) dissolved in toluene (9 mL) was added dropwise and stirred at 35°C. overnight. The resultant mixture was added dropwise at 0° C. to amixed solution of a 10% sodium hydrogen carbonate (22 mL) and a 10%sodium carbonate (22 mL). Toluene (22 mL) was added to separate anorganic phase. After dried over sodium sulfate, the organic phase wasfiltrated. The solvent was removed under reduced pressure to obtain1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (3.76 g, yield66.3%).

¹H-NMR (CDCl₃, δppm): 1.55 (s, 6H), 1.57 (s, 6H), 3.77 (s, 1H),7.27-7.42 (m, 9H), 7.54-7.63 (m, 6H)

Mass Spectrum (EI-MS, m/z): 380 (M⁺)

Synthesis of Complex 9

Under a nitrogen atmosphere, to a toluene solution (28 mL) of1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.42 g, 4.45 mmol)and triethylamine (2.25 g, 22.24 mmol), a 1.55 M hexane solution ofn-butyllithium (3.44 mL, 5.34 mmol) was added dropwise at −78° C. Afterthe mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 3 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (0.93 g, 4.89 mmol)dissolved in toluene (5 mL) was added dropwise at the same temperature.After the mixture was warmed and the internal temperature was set to 35°C., stirring was performed at the same temperature for one hour. Aftercompletion of the reaction, the solvent was removed under reducedpressure. The residue, to which heptane was added, was filtrated toremove insoluble materials. The solvent was removed under reducedpressure. Pentane was added and the resultant solid was filtrated andwashed with a small amount of pentane, and then, dried under reducedpressure to obtain complex 9 (0.07 g, yield 3.1%) as an orange solid.Furthermore, to the insoluble materials removed by adding heptane,toluene was added and filtrated to further remove insoluble matter intoluene. The solvent was removed from the filtrate under reducedpressure. Pentane was added and the resultant solid was filtrate and,washed with a small amount of pentane, and then, dried under reducedpressure to obtain complex 9 (0.34 g, yield 14.5%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 2.05 (s, 6H), 2.36 (s, 6H), 7.32-7.49 (m, 9H),7.59-7.65 (m, 6H)

¹³C-NMR (CDCl₃, δppm): 14.48, 17.76, 127.96, 130.07, 132.99, 136.93,142.35, 146.04

Mass Spectrum (EI-MS, m/z): 532 (M⁺)

Example 10 Synthesis of[1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 10”) Synthesis of1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.83 g, 34.48 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (85mL) were mixed. This mixture was heated to 50° C. and aniline (0.21 g,2.30 mmol) was added, and then, stirred at 50° C. for one hour. To this,a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.09 g, 25.28mmol) dissolved in tetrahydrofuran (21 mL) was added dropwise andstirred at 50° C. for 2 hours, and then was cooled to 0° C. To thissolution, a solution of chlorotri(4-n-butylphenyl)silane (10.65 g, 22.99mmol) dissolved in toluene (21 mL) was added dropwise and stirred at 35°C. The resultant mixture was added dropwise at 0° C. to a mixed solutionof a 10% sodium hydrogen carbonate (53 mL) and a 10% sodium carbonate(53 mL). Toluene (53 mL) was added to separate an organic phase, and theorganic phase was dried over sodium sulfate and filtrated. The solventwas removed under reduced pressure. Purification was performed by silicagel column chromatography to obtain1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (6.42 g,yield 50.9%).

¹H-NMR (CDCl₃, δppm): 0.92 (t, J=7.3 Hz, 9H), 1.15-1.43 (m, 6H),1.50-1.67 (m, 6H), 1.52 (s, 6H), 1.57 (s, 6H), 2.54-2.65 (m, 6H), 3.71(s, 1H), 7.12 (d, J=8.0 Hz, 6H), 7.47 (d, J=8.0 Hz, 6H)

¹³C-NMR (CDCl₃, δppm): 11.00, 13.96, 14.79, 22.40, 33.43, 35.65, 51.57,127.48, 127.67, 131.26, 135.24, 135.69, 143.80

Mass Spectrum (EI-MS, m/z): 548 (M⁺)

Synthesis of Complex 10

Under a nitrogen atmosphere, to a toluene solution (60 mL) of1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (2.98 g,5.43 mmol) and triethylamine (2.75 g, 27.13 mmol), a 1.67 M hexanesolution of n-butyllithium (3.90 mL, 6.51 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at 35° C. for 5.5 hours. The resultant mixturewas cooled to −78° C. and a solution of titanium tetrachloride (1.13 g,5.97 mmol) dissolved in toluene (6 mL) was added dropwise at the sametemperature. After the mixture was warmed again to room temperature,stirring was performed at room temperature overnight. After completionof the reaction, the solvent was removed under reduced pressure. Theresidue, to which heptane was added, was filtrated to remove insolublematerials. The solvent was removed under reduced pressure.Hexamethyldisiloxane was added and cooled to −20° C. The resultant solidwas filtrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 10 (0.19 g, yield 5.0%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 0.92 (t, J=7.3 Hz, 9H), 1.29-1.42 (m, 6H),1.55-1.66 (m, 6H), 2.03 (s, 6H), 2.35 (s, 6H), 2.62 (t, J=7.6 Hz, 6H),7.18 (d, J=8.0 Hz, 6H), 7.51 (d, J=8.0 Hz, 6H)

¹³C-NMR (CDCl₃, δppm): 13.96, 14.46, 17.72, 22.40, 33.32, 35.66, 128.02,129.96, 136.53, 136.89, 142.28, 144.81, 146.22

Mass Spectrum (EI-MS, m/z): 700 (M⁺)

Example 11 Synthesis of[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 11”) Synthesis of1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (23mL) were mixed. This mixture was heated to 50° C. and aniline (0.13 g,1.36 mmol) was added and stirred at 50° C. for one hour. To this, asolution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.83 g, 15.00 mmol)dissolved in tetrahydrofuran (6 mL) was added dropwise and stirred at50° C. for 3.5 hours, and then was cooled to 0° C. To this solution, asolution of chlorotris(3,5-dimethylphenyl)silane (5.17 g, 13.64 mmol)dissolved in toluene (6 mL) was added dropwise and stirred at roomtemperature for 3 hours, and thereafter, stirred at 50° C. for 22 hours.The resultant mixture was added dropwise at 0° C. to 10% aqueous sodiumcarbonate solution (40 mL). Toluene was added to separate an organicphase, and the organic phase was washed with water (50 mL) twice andfurther washed with saturated brine (50 mL). The organic phase was driedover sodium sulfate and filtrated. The solvent was removed under reducedpressure. After purification was performed by silica gel columnchromatography, hexane of 50° C. was added to the resultant solid, andfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. The resultant solid was washed with a small amount ofhexane and then dried under reduced pressure to obtain1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (1.49g, yield 23.4%).

¹H-NMR (CDCl₃, δppm): 1.54 (s, 6H), 1.60 (s, 6H), 2.27 (s, 18H), 3.73(s, 1H), 6.98 (s, 3H), 7.17 (s, 6H)

Mass Spectrum (EI-MS, m/z): 464 (M⁺)

Synthesis of Complex 11

Under a nitrogen atmosphere, to a toluene solution (20 mL) of1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (0.93g, 2.00 mmol) and triethylamine (1.01 g, 10.00 mmol), a 1.67 M hexanesolution of n-butyllithium (1.32 mL, 2.20 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 5 hours. The resultantmixture was cooled to −78° C. and a solution of titanium tetrachloride(0.42 g, 2.20 mmol) dissolved in toluene (2 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature overnight. Aftercompletion of the reaction, the solvent was removed under reducedpressure. Thereafter, the residue, to which heptane was added, wasfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. Furthermore, to the resultant residue, diethyl etherwas added and filtrated to remove insoluble materials. The solvent wasremoved from the filtrate under reduced pressure. Pentane was added andcooled to −20° C. The resultant solid substance was filtrated and washedwith a small amount of pentane, and then dried under reduced pressure toobtain complex 11 (0.03 g, yield 2.7%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06(s, 3H), 7.20 (s, 6H)

¹³C-NMR (CDCl₃, δppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60,137.03, 142.26, 146.34

Mass Spectrum (EI-MS, m/z): 616 (M⁺)

Example 12 Synthesis of[1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 12”) Synthesis of1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.96 g, 40.00 mmol as pure sodium hydride) andtetrahydrofuran (43 mL) were mixed. This mixture was heated to 50° C.and aniline (0.25 g, 2.67 mmol) was added and stirred at 50° C. for 2.5hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.42 g, 28.00 mmol) dissolved in tetrahydrofuran (11 mL) was addeddropwise and stirred at 50° C. for 2.5 hours, and then was cooled to 0°C. To this solution, a solution of chlorodimethyl(4-methoxyphenyl)silane(5.35 g, 26.67 mmol) dissolved in toluene (11 mL) was added dropwise andstirred at room temperature overnight. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (56 ml).Toluene (80 mL) was added to separate an organic phase, and the organicphase was washed with water (80 mL) twice, and further washed withsaturated brine (50 mL). After dried over sodium sulfate, the organicphase was filtrated. The solvent was removed under reduced pressure toobtain1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(7.30 g, yield 95.5%).

¹H-NMR (CDCl₃, δppm): 0.18 (s, 6H), 1.75 (s, 6H), 1.77 (s, 6H), 3.06 (s,1H), 3.83 (s, 3H), 6.90 (d, J=8.6 Hz, 2H), 7.39 (d, J=8.7 Hz, 2H)

Mass Spectrum (EI-MS, m/z): 286 (M⁺)

Synthesis of Complex 12

Under a nitrogen atmosphere, to a toluene solution (48 mL) of1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(2.01 g, 7.00 mmol) and triethylamine (3.54 g, 35.00 mmol), a 1.65 Mhexane solution of n-butyllithium (5.09 mL, 8.40 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 2 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (1.46 g, 7.70 mmol) dissolved in toluene (8 mL) was addeddropwise at the same temperature. After the mixture was gradually warmedto room temperature, stirring was performed at room temperatureovernight. After completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 12 (0.48 g, yield 15.6%)as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.73 (s, 6H), 2.32 (s, 6H), 2.39 (s, 6H), 3.81 (s,3H), 6.90 (d, J=8.7 Hz, 2H), 7.39 (d, J=8.7 Hz, 2H)

¹³C-NMR (CDCl₃, δppm): 0.50, 14.35, 17.81, 55.20, 114.00, 128.16,135.71, 139.59, 142.33, 145.04, 160.98

Mass Spectrum (EI-MS, m/z): 438 (M⁺)

Example 13 Synthesis of[1-benzyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 13”) Synthesis of1-benzyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.51 g, 21.20 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (35mL) were mixed. This mixture was heated to 50° C. and aniline (0.13 g,1.41 mmol) was added and stirred at 50° C. for one hour. To this, asolution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.90 g, 15.55 mmol)dissolved in tetrahydrofuran (9 mL) was added dropwise and stirred at50° C. for 2 hours, and then was cooled to 0° C. To this solution, asolution of benzylchlorodiphenylsilane (4.37 g, 14.13 mmol) dissolved intoluene (9 mL) was added dropwise and stirred at 35° C. The resultantmixture was added dropwise at 0° C. to a mixed solution of a 10% sodiumhydrogen carbonate (22 mL) and a 10% sodium carbonate (22 mL). Toluene(22 mL) was added to separate an organic phase, and the organic phasewas dried over sodium sulfate and filtrated. The solvent was removedunder reduced pressure. Purification was performed by silica gel columnchromatography to obtain1-benzyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (2.59 g, yield46.4%).

¹H-NMR (CDCl₃, δppm): 1.53 (s, 6H), 1.76 (s, 6H), 2.73 (s, 2H), 3.54 (s,1H), 6.72-6.79 (m, 2H), 6.95-7.02 (m, 3H), 7.17-7.40 (m, 10H)

Mass Spectrum (EI-MS, m/z): 394 (M⁺)

Synthesis of Complex 13

Under a nitrogen atmosphere, to a toluene solution (26 mL) of1-benzyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.28 g, 3.24mmol) and triethylamine (1.64 g, 16.21 mmol), a 1.67 M hexane solutionof n-butyllithium (2.33 mL, 3.89 mmol) was added dropwise at −78° C.After the mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 3.5 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (0.68 g, 3.57 mmol)dissolved in toluene (4 mL) was added dropwise at the same temperature.After the mixture was warmed to room temperature, the mixture wasstirred at room temperature overnight. After completion of the reaction,the solvent was removed under reduced pressure. Thereafter, the residue,to which heptane was added, was filtrated to remove insoluble materials.The solvent was removed under reduced pressure. Pentane was added andthe resultant solid was filtrated and washed with a small amount ofpentane, and then, dried under reduced pressure to obtain complex 13(47.9 mg, yield 2.7%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 2.20 (s, 6H), 2.37 (s, 6H), 3.28 (s, 2H),6.88-6.94 (m, 2H), 7.03-7.08 (m, 3H), 7.24-7.44 (m, 10H)

¹³C-NMR (CDCl₃, δppm): 14.44, 17.80, 24.38, 124.85, 127.86, 128.09,129.53, 130.05, 132.63, 136.47, 136.65, 137.49, 142.49, 145.41

Mass Spectrum (EI-MS, m/z): 455 (M⁺-Bn)

Example 14 Synthesis of[9-dimethylphenylsilyl-octahydrofluorenyl]titanium trichloride(Hereinafter, Referred to as “Complex 14”) Synthesis of9-dimethylphenylsilyl-octahydrofluorene

Under a nitrogen atmosphere, octahydrofluorenyllithium (1.50 g, 8.32mmol) and tetrahydrofuran (30 mL) were mixed. This mixture was cooled to−30° C. To this solution, a solution of chlorodimethylphenylsilane (1.56g, 9.16 mmol) dissolved in toluene (8 mL) was added dropwise and stirredat room temperature. The resultant mixture was added dropwise at 0° C.to a mixed solution of a 10% sodium hydrogen carbonate (8 mL) and a 10%sodium carbonate (8 mL). Toluene (8 mL) was added to separate an organicphase, and the organic phase was dried over sodium sulfate andfiltrated. Thereafter, the solvent was removed under reduced pressureand purification was performed by silica gel column chromatography toobtain 9-dimethylphenylsilyl-octahydrofluorene (1.75 g, yield 67.9%).

¹H-NMR (CDCl₃, δppm): 0.22 (s, 6H), 1.41-1.58 (m, 4H), 1.60-1.80 (m,4H), 2.08 (br s, 4H), 2.16 (br s, 4H), 3.00 (s, 1H), 7.28-7.38 (m, 3H),7.43-7.51 (m, 2H)

Mass Spectrum (EI-MS, m/z): 308 (M⁺)

Synthesis of Complex 14

Under a nitrogen atmosphere, to a toluene solution (33 mL) of(9-dimethylphenylsilyl-octahydrofluorene) (1.66 g, 5.38 mmol) andtriethylamine (2.72 g, 26.88 mmol), a 1.67 M hexane solution ofn-butyllithium (3.86 mL, 6.45 mmol) was added dropwise at −78° C. Afterthe mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 3.5 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (1.12 g, 5.91 mmol)dissolved in toluene (6 mL) was added dropwise at the same temperature.After the mixture was warmed again, the mixture was stirred at roomtemperature overnight. After completion of the reaction, the solvent wasremoved under reduced pressure. Thereafter, the residue, to whichheptane was added, was filtrated to remove insoluble materials. Thesolvent was removed under reduced pressure. Pentane was added and theresultant solid was filtrated and washed with a small amount of pentane,and then, dried under reduced pressure to obtain complex 14 (0.17 g,yield 6.7%) as an orange solid. Furthermore, to the insoluble materialsremoved by adding heptane described above toluene was added andfiltrated to further remove toluene-insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 14 (0.40 g, yield 16.3%)as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.73 (s, 6H), 1.56-1.77 (m, 4H), 1.82-2.00 (m,4H), 2.49-2.67 (m, 4H), 3.08-3.22 (m, 2H), 3.45 (dt, J=17.1, 6.0 Hz,2H), 7.30-7.40 (m, 3H), 7.40-7.46 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −0.33, 21.47, 22.46, 25.35, 29.09, 128.05,129.56, 134.01, 137.17, 137.88, 144.01, 147.11

Mass Spectrum (EI-MS, m/z): 460 (M⁺)

Example 15 Synthesis of [1-dimethylphenylsilyl-indenyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 15”) Synthesis of1-dimethylphenylsilylindene

Under a nitrogen atmosphere, to a tetrahydrofuran solution (34 mL) ofindene (1.85 g, 15.93 mmol), a 1.67 M hexane solution (10 mL, 16.7 mmol)of n-butyllithium was added dropwise at −78° C. After the mixture wasgradually warmed to room temperature, stirring was performed at roomtemperature for 2 hours. The resultant mixture was added dropwise to amixed solution of a 10% sodium hydrogen carbonate (17 mL) and a 10%sodium carbonate (17 mL) at 0° C. Toluene (17 mL) was added to separatean organic phase, and the organic phase was dried over sodium sulfateand filtrated. The solvent was removed under reduced pressure andpurification was performed by silica gel column chromatography to obtain1-dimethylphenylsilylindene (3.07 g, yield 76.9%).

Synthesis of (1-dimethylphenylsilylindenyl)lithium

Under a nitrogen atmosphere, to a hexane solution (30 mL) of1-dimethylphenylsilylindene (1.30 g, 5.19 mmol), a 1.67 M hexanesolution (3.7 mL, 6.18 mmol) of n-butyllithium was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 2 hours. After thecompletion of the reaction, filtration and washing with hexane wereperformed to obtain (1-dimethylphenylsilylindenyl)lithium (1.17 g, yield88%).

Synthesis of 1,3-bis(dimethylphenylsilyl)indene

Under a nitrogen atmosphere, to a tetrahydrofuran solution (20 mL) of(1-dimethylphenylsilylindenyl)lithium (0.96 g, 3.75 mmol), a solution ofchlorodimethylphenylsilane (0.73 g, 4.25 mmol) dissolved intetrahydrofuran (5 mL) was added dropwise at −78° C. After the mixturewas warmed, stirring was performed at room temperature for 4 hours andthereafter stirring was performed at 35° C. The resultant mixture wasadded dropwise at 0° C. to a mixed solution of a 10% sodium hydrogencarbonate (15 mL) and a 10% sodium carbonate (15 mL). Toluene (20 mL)was added to separate an organic phase, and the organic phase was driedover sodium sulfate and filtrated. The solvent was removed under reducedpressure and purification was performed by silica gel columnchromatography to obtain 1,3-bis(dimethylphenylsilyl)indene (0.65 g,yield 45.1%).

Synthesis of Complex 15

Under a nitrogen atmosphere, to a dichloromethane solution (8 mL) oftitanium tetrachloride (0.34 g, 1.79 mmol), a dichloromethane solution(8 mL) of 1,3-bis(dimethylphenylsilyl)indene (0.65 g, 1.69 mmol) wasadded dropwise at room temperature, and thereafter, stirred at roomtemperature for 17 days. After the completion of the reaction, thesolvent was removed under reduced pressure. Thereafter, to the residue,pentane was added at −20° C. to obtain a solid. The resultant solid waswashed with a small amount of pentane and dried under reduced pressureto obtain complex 15 (0.25 g, yield 37.0%) as a red brown solid.

¹H-NMR (CDCl₃, δppm): 0.83 (s, 3H), 0.83 (s, 3H), 7.26-7.28 (m, 1H),7.36-7.55 (m, 8H), 7.73-7.76 (m, 1H), 7.81-7.84 (m, 1H)

¹³C-NMR (CDCl₃, δppm): −1.93, −1.44, 120.20, 126.75, 128.18, 128.67,129.54, 129.58, 129.92, 130.14, 133.65, 134.13, 134.86, 135.27, 135.97

Mass Spectrum (EI-MS, m/z): 402 (M⁺)

Example 16 Synthesis of[1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 16”) Synthesis of1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.82 g, 34.09 mmol in terms of pure sodium hydride) andtetrahydrofuran (39 mL) were mixed. This mixture was heated to 50° C.and aniline (0.21 g, 2.27 mmol) was added and stirred at 50° C. for 2hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.06 g, 25.00 mmol) dissolved in tetrahydrofuran (10 mL) was addeddropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.To this solution, a solution ofchlorodimethyl(2,4,6-trimethylphenyl)silane (4.84 g, 22.73 mmol)dissolved in toluene (10 mL) was added dropwise and stirred at roomtemperature overnight. The resultant mixture was added dropwise at 0° C.to a 10% aqueous sodium carbonate solution (50 ml). Toluene (70 mL) wasadded to separate an organic phase, and the organic phase was washedwith water (70 mL) twice and further washed with saturated brine (50mL). After dried over sodium sulfate, the organic phase was filtrated.The solvent was removed under reduced pressure to obtain1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(5.93 g, yield 87.3%).

¹H-NMR (CDCl₃, δppm): 0.20 (s, 6H), 1.69 (s, 6H), 1.81 (s, 6H), 2.26 (s,3H), 2.41 (s, 6H), 3.28 (s, 1H), 6.81 (s, 2H)

Mass Spectrum (EI-MS, m/z): 298 (M⁺)

Synthesis of Complex 16

Under a nitrogen atmosphere, to a toluene solution (32 mL) of1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(1.49 g, 5.00 mmol) and triethylamine (2.53 g, 25.00 mmol), a 1.65 Mhexane solution of n-butyllithium (3.33 mL, 5.50 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 4 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (1.04 g, 5.50 mmol) dissolved in toluene (6 mL) was addeddropwise. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature overnight. After thecompletion of the reaction, the solvent was removed under reducedpressure. The residue, to which heptane was added, was filtrated toremove insoluble materials. The solvent was removed under reducedpressure. Pentane was added and cooled to −20° C. The resultant solidwas filtrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 16 (0.21 g, yield 9.2%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 0.83 (s, 6H), 2.21 (s, 6H), 2.24 (s, 3H), 2.32 (s,6H), 2.36 (s, 6H), 6.78 (s, 2H)

¹³C-NMR (CDCl₃, δppm): 4.90, 14.29, 17.75, 20.90, 24.63, 129.58, 130.67,139.43, 142.35, 143.70, 144.10, 144.67

Mass Spectrum (EI-MS, m/z): 450 (M⁻)

Example 17 Synthesis of[1-dimethylphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride(Hereinafter, Referred to as “Complex 17”) Synthesis of(2-methyltetrahydroindenyl)lithium

Under a nitrogen atmosphere, 3,3a,4,5,6,7-hexahydro-2(2H)-indenone (3.00g, 22.04 mmol) and tetrahydrofuran (30 mL) were mixed. This mixture wascooled to −78° C. and a 1.07 M diethyl ether solution (34.72 mL, 37.15mmol) of methyllithium was added dropwise and stirred at roomtemperature. The resultant mixture was added dropwise 0° C. to asaturated aqueous ammonium chloride solution. Toluene was added toseparate an oil phase, and the organic phase was dried over sodiumsulfate and filtrated. The solvent was removed under reduced pressure.To the resultant mixture, tetrahydrofuran (30 mL) was added. Thismixture was cooled to 0° C. and a 3% aqueous hydrochloric acid solution(9 mL) was added and stirred at room temperature for 2 hours. Tolueneand water were added to separate an organic phase, and the organic phasewas washed with a saturated aqueous sodium chloride solution. Theorganic phase was dried over magnesium sulfate, and then filtrated. Thesolvent was removed under reduced pressure. To the resultant mixture,hexane (60 mL) was added. This mixture was cooled to −78° C., a 1.67 Mhexane solution (15.2 mL, 25.36 mmol) of n-butyllithium was addeddropwise. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 2 hours. The solvent wasremoved by filtration and the resultant solid substance was washed withhexane to obtain (2-methyltetrahydroindenyl)lithium (2.10 g, yield 68%).

Synthesis of 1-dimethylphenylsilyl-2-methyltetrahydroindene

Under a nitrogen atmosphere, (2-methyltetrahydroindenyl)lithium (1.50 g,10.70 mmol) and tetrahydrofuran (25 mL) were mixed. This mixture wascooled to −78° C. To this solution, a solution ofchlorodimethylphenylsilane (2.19 g, 12.84 mmol) dissolved intetrahydrofuran (5 mL) was added dropwise and stirred at roomtemperature for 2 hours. To the resultant mixture, a mixed solution of a10% sodium hydrogen carbonate (10 mL) and a 10% sodium carbonate (10 mL)was added dropwise at 0° C. Toluene (10 mL) was added to separate anorganic phase, and the organic phase was dried over sodium sulfate andfiltrated. The solvent was removed under reduced pressure andpurification was performed by silica gel column chromatography to obtain1-dimethylphenylsilyl-2-methyltetrahydroindene (1.94 g, yield 67.5%).

¹H-NMR (CDCl₃, δppm): 0.22 (s, 3H), 0.23 (s, 3H), 1.46-1.72 (m, 4H),1.81 (s, 3H), 2.07 (br, 2H), 2.24 (br, 2H), 3.11 (s, 1H), 5.97 (s, 1H),7.31-7.38 (m, 3H), 7.46-7.54 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −4.05, −4.05, 16.93, 23.29, 23.73, 24.54, 26.63,53.36, 127.57, 128.94, 129.16, 133.67, 137.38, 137.44, 138.56, 141.85

Mass Spectrum (EI-MS, m/z): 268 (M⁺)

Synthesis of Complex 17

Under a nitrogen atmosphere, to a toluene solution (30 mL) of1-dimethylphenylsilyl-2-methyltetrahydroindene (1.50 g, 5.59 mmol) andtriethylamine (2.83 g, 27.95 mmol), a 1.67 M hexane solution ofn-butyllithium (4.02 mL, 6.71 mmol) was added dropwise at −78° C. Afterthe mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 3 hours. The resultant mixture was cooled to−78° C. and a solution of titanium tetrachloride (1.17 g, 6.15 mmol)dissolved in toluene (6 mL) was added dropwise at the same temperature.The mixture was warmed and stirring was performed at room temperatureovernight. After completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 17 (0.17 g, yield 7.0%)as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.73 (s, 6H), 1.60-1.74 (m, 2H), 1.77-1.93 (m,2H), 2.49 (s, 3H), 2.54-2.79 (m, 2H), 3.17-3.41 (m, 2H), 7.33-7.47 (m,5H)

¹³C-NMR (CDCl₃, δppm): −0.34, −0.32, 20.22, 21.54, 22.38, 26.96, 28.54,128.10, 128.35, 129.66, 133.99, 136.97, 137.71, 144.95, 147.06, 148.14

Mass Spectrum (EI-MS, m/z): 405 (M⁺-Me)

Example 18 Synthesis of[1-dimethyl(1-naphthyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 18”) Synthesis of1-dimethyl(1-naphthyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.66 g, 27.27 mmol in terms of pure sodium hydride) andtetrahydrofuran (31 mL) were mixed. This mixture was heated to 50° C.and aniline (0.17 g, 1.82 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(2.44 g, 20.00 mmol) dissolved in tetrahydrofuran (8 mL) was addeddropwise and stirred at 50° C. for 2.5 hours, and then was cooled to 0°C. To this solution, a solution of chlorodimethyl(1-naphthyl)silane(4.01 g, 18.18 mmol) dissolved in toluene (8 mL) was added dropwise andstirred at room temperature overnight. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (40 ml).Toluene (50 mL) was added to separate an organic phase, and the organicphase was washed with water (50 mL) twice and further washed withsaturated brine (50 mL). The organic phase was dried over sodium sulfateand filtrated. The solvent was removed under reduced pressure andpurification was performed by silica gel column chromatography to obtain1-dimethyl(1-naphthyl)silyl-2,3,4,5-tetramethylcyclopentadiene (3.24 g,yield 58.2%).

¹H-NMR (CDCl₃, δppm): 0.34 (s, 6H), 1.66 (s, 6H), 1.81 (s, 6H), 3.46 (s,1H), 7.40-7.66 (m, 4H), 7.82-7.95 (m, 2H), 8.24 (d, J=7.9 Hz, 1H)

Mass Spectrum (EI-MS, m/z): 306 (M⁺)

Synthesis of Complex 18

Under a nitrogen atmosphere, to a toluene solution (31 mL) of1-dimethyl(1-naphthyl)silyl-2,3,4,5-tetramethylcyclopentadiene (1.38 g,4.50 mmol) and triethylamine (2.28 g, 22.50 mmol), a 1.65 M hexanesolution of n-butyllithium (3.00 mL, 4.95 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 4.5 hours. The resultantmixture was cooled to −78° C., and a solution of titanium tetrachloride(0.94 g, 4.95 mmol) dissolved in toluene (5 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature overnight. Afterthe completion of the reaction, the solvent was removed under reducedpressure. Thereafter, the residue, to which heptane was added, wasfiltrated to remove insoluble materials. The solvent was removed fromthe filtrate under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 18 (0.57 g, yield 27.7%)as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.94 (s, 6H), 2.31 (s, 6H), 2.40 (s, 6H),7.30-7.53 (m, 3H), 7.62-7.77 (m, 2H), 7.88 (t, J=8.2 Hz, 2H)

¹³C-NMR (CDCl₃, δppm): 1.43, 14.23, 17.72, 125.31, 125.49, 125.80,127.34, 129.34, 130.57, 133.46, 134.21, 135.36, 136.46, 139.92, 142.31,144.49

Mass Spectrum (EI-MS, m/z): 458 (M⁻)

Example 19 Synthesis of[1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 19”) Synthesis of1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.47 g, 19.50 mmol in terms of pure sodium hydride) andtetrahydrofuran (22 mL) were mixed. This mixture was heated to 50° C.and aniline (0.14 g, 1.50 mmol) was added and stirred at 50° C. for 2hours. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(1.83 g, 15.00 mmol) dissolved in tetrahydrofuran (7 mL) was addeddropwise and stirred at 50° C. for 4.5 hours, was cooled to roomtemperature, and then was added dropwise to a solution of(3,5-bis(trifluoromethyl)phenyl)dimethylsilane (4.60 g, 15.00 mmol)dissolved in toluene (22 mL) that had been cooled to 0° C. and stirredat room temperature overnight. The resultant mixture was added dropwiseat 0° C. to a 10% aqueous sodium carbonate solution (30 ml). Toluene (50mL) was added to separate an organic phase, and the organic phase waswashed with water (50 mL) twice and further washed with saturated brine(50 mL). The organic phase was dried over sodium sulfate and filtrated.The solvent was removed under reduced pressure and purification wasperformed by silica gel column chromatography to obtain1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene(3.20 g, yield 54.3%).

¹H-NMR (CDCl₃, δppm): 0.15 (s, 6H), 1.40 (s, 6H), 1.57 (s, 6H), 2.82 (s,1H), 7.49 (s, 2H), 7.57 (s, 1H)

Mass Spectrum (EI-MS, m/z): 392 (M⁺)

Synthesis of Complex 19

Under a nitrogen atmosphere, to a toluene solution (35 mL) of1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene(1.37 g, 3.50 mmol) and triethylamine (1.77 g, 17.50 mmol), a 1.65 Mhexane solution of n-butyllithium (2.33 mL, 3.85 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 5 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (0.73 g, 3.85 mmol) dissolved in toluene (4 mL) was addeddropwise at the same temperature. After the mixture was gradually warmedto room temperature, stirring was performed at room temperatureovernight. After the completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and cooled to −20° C.The resultant solid was filtrated and washed with a small amount ofpentane, and then, dried under reduced pressure to obtain complex 19(0.13 g, yield 6.8%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.83 (s, 6H), 2.35 (s, 6H), 2.38 (s, 6H), 7.88 (s,3H)

Mass Spectrum (EI-MS, m/z): 544 (M⁻)

Example 20 Synthesis of[3-methyl-1-dimethylphenylsilylcyclopentadienyl]titanium trichloride(Hereinafter, Referred to as “Complex 20”) Synthesis of1-dimethylphenylsilyl-methylcyclopentadiene

Under a nitrogen atmosphere, to a tetrahydrofuran solution (30 mL) ofmethylcyclopentadienyllithium (1.50 g, 17.43 mmol), a solution ofdimethylphenylsilyl chloride (3.27 g, 19.17 mmol) dissolved in toluene(16 mL) was added dropwise at −30° C. The mixture was heated to roomtemperature and stirred overnight. The resultant mixture was addeddropwise to a mixed solution of a 10% sodium hydrogen carbonate (16 mL)and a 10% sodium carbonate (16 mL) at 0° C. Toluene (16 mL) was added toseparate an organic phase, and the organic phase was dried over sodiumsulfate and then filtrated. The solvent was removed under reducedpressure to obtain 1-dimethylphenylsilyl-methylcyclopentadiene (3.47 g,yield 92.8%) as a mixture of regioisomers.

¹H-NMR (CDCl₃, δppm) (major isomer): 0.17 (br s, 6H), 2.03 (s, 3H), 3.46(s, 1H), 6.07 (s, 1H), 6.42 (s, 2H), 7.32-7.40 (m, 3H), 7.51-7.57 (m,2H)

Mass Spectrum (EI-MS, m/z): 214 (M⁺)

Synthesis of 1-dimethylphenylsilyl-methylcyclopentadienyllithium

Under a nitrogen atmosphere, to a hexane solution (52 mL) of1-dimethylphenylsilyl-methylcyclopentadiene (2.58 g, 12.02 mmol), a 1.67M hexane solution of n-butyllithium (8.64 mL, 14.43 mmol) was addeddropwise at 0° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at 40° C. Diethyl ether was addedand the resultant white solid was filtrated and washed with a smallamount of pentane, and then, dried under reduced pressure to obtain1-dimethylphenylsilyl-methylcyclopentadienyllithium (2.31 g, yield86.1%) as a white solid.

Synthesis of 3-methyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene

Under a nitrogen atmosphere, a tetrahydrofuran solution (26 mL) of1-dimethylphenylsilyl-methylcyclopentadienyllithium (1.30 g, 5.90 mmol),a solution of dimethylphenylsilyl chloride (1.11 g, 6.49 mmol) dissolvedin toluene (5 mL) was added dropwise at −30° C. The mixture was heatedto room temperature and stirring was performed overnight. The resultantmixture was added dropwise at 0° C. to a mixed solution of a 10% sodiumhydrogen carbonate (13 mL) and a 10% sodium carbonate (13 mL). Toluene(13 mL) was added to separate an organic phase, and the organic phasewas dried over sodium sulfate and then filtrated. The solvent wasremoved under reduced pressure and purification was performed by silicagel column chromatography to obtain3-methyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene (0.72 g, yield35.0%).

¹H-NMR (CDCl₃, δppm): −0.10 (s, 6H), −0.09 (s, 6H), 2.02 (s, 3H), 6.25(s, 1H), 6.48 (d, J=4.6 Hz, 1H), 6.56 (d, J=4.6 Hz, 1H), 7.25-7.37 (m,6H), 7.38-7.45 (m, 4H)

Mass Spectrum (EI-MS, m/z): 348 (M⁺)

Synthesis Complex 20

Under a nitrogen atmosphere, to a toluene solution (15 mL) of3-methyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene (0.72 g, 2.05mmol), a solution of titanium tetrachloride (0.39 g, 2.05 mmol)dissolved in toluene (4 mL) was added dropwise at −30° C. The mixturewas warmed to room temperature and stirring was performed overnight.After the completion of the reaction, the solvent was removed underreduced pressure and then pentane was added. The supernatant was removedat −20° C. This operation was repeated four times. The resultant residuewas dried under reduced pressure to obtain complex 20 (0.39 g, yield51.4%) as a brown oil.

¹H-NMR (CDCl₃, δppm): 0.67 (s, 3H), 0.67 (s, 3H), 2.47 (s, 3H),6.87-6.91 (m, 1H), 7.01-7.05 (m, 1H), 7.13-7.16 (m, 1H), 7.34-7.43 (m,3H), 7.48-7.54 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −2.46,-2.29, 17.35, 127.72, 128.11, 129.49,129.83, 129.87, 133.91, 136.03, 141.84, 143.62

Mass Spectrum (EI-MS, m/z): 366 (M⁻)

Example 21 Synthesis of[1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 21”) Synthesis of1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadiene

Under a nitrogen atmosphere, (1,2,4-trimethylcyclopentadienyl)lithium(2.10 g, 18.40 mmol) and tetrahydrofuran (90 mL) were mixed. Thismixture was cooled to −78° C. To this solution, a solution ofchlorodimethylphenylsilane (1.89 g, 11.04 mmol) dissolved intetrahydrofuran (10 mL) was added dropwise and stirred at roomtemperature for 2 hours. The resultant mixture was added dropwise at 0°C. to a mixed solution of a 10% sodium hydrogen carbonate and a 10%sodium carbonate. Toluene was added to separate an organic phase, andthe organic phase was dried over sodium sulfate and filtrated. Thesolvent was removed under reduced pressure and purification wasperformed by silica gel column chromatography to obtain1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadiene (0.99 g, yield37%).

¹H-NMR (CDCl₃, δppm): 0.20 (s, 3H), 0.23 (s, 3H), 1.72 (s, 3H), 1.79 (s,3H), 1.81 (s, 3H), 3.17 (s, 1H), 5.97 (s, 1H), 7.34-7.37 (m, 3H),7.49-7.57 (m, 2H)

Mass Spectrum (EI-MS, m/z): 242 (M⁺)

Synthesis of Complex 21

Under a nitrogen atmosphere, to a toluene solution (20 mL) of1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadiene (0.98 g, 4.04 mmol)and triethylamine (2.05 g, 20.22 mmol), a 1.65 M hexane solution ofn-butyllithium (2.9 mL, 4.85 mmol) was added dropwise at −78° C. Afterthe mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 4 hours. The resultant mixture was cooled to−78° C., and a solution of titanium tetrachloride (0.84 g, 4.45 mmol)dissolved in toluene (4.5 mL) was added dropwise at the sametemperature. The mixture was warmed and stirring was performed at roomtemperature overnight. After the completion of the reaction, the solventwas removed under reduced pressure. Thereafter, the residue, to whichheptane was added, was filtrated to remove insoluble materials. Thesolvent was removed under reduced pressure. Pentane was added and theresultant solid was filtrated and washed with a small amount of pentane.To the solid substance, toluene was added and filtrated to removeinsoluble materials. The solvent was removed under reduced pressure.Pentane was added and the resultant solid was filtrated and washed witha small amount of pentane and then concentrated under reduced pressureto obtain complex 21 (0.037 g, yield 2.3%) as an orange solid.

¹H-NMR (CDCl₃, δppm): 0.74 (s, 3H), 0.75 (s, 3H), 2.33 (s, 3H), 2.36 (s,3H), 2.47 (s, 3H), 6.75 (s, 1H), 7.33-7.47 (m, 5H)

Mass Spectrum (EI-MS, m/z): 394 (M⁻)

Example 22 Synthesis of[1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 22”) Synthesis of1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.82 g, 34.09 mmol in terms of pure sodium hydride) andtetrahydrofuran (39 mL) were mixed. This mixture was heated to 50° C.and aniline (0.21 g, 2.27 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.06 g, 25.00 mmol) dissolved in tetrahydrofuran (10 mL) was addeddropwise and stirred at 50° C. for 4 hours, and then was cooled to 0° C.To this solution, a solution of (9-anthryl)chlorodimethylsilane (6.16 g,22.73 mmol) dissolved in toluene (10 mL) was added dropwise and stirredat room temperature overnight. The resultant mixture was added dropwiseat 0° C. to a 10% aqueous sodium carbonate solution (50 ml). Toluene (70mL) was added to separate an organic phase, and the organic phase waswashed with water (80 mL) twice and further washed with saturated brine(50 mL). The organic phase was dried over sodium sulfate and filtrated.The solvent was removed under reduced pressure and purification wasperformed by silica gel column chromatography to obtain1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene (4.41 g,yield 54.4%).

¹H-NMR (CDCl₃, δppm): 0.49 (s, 6H), 1.68 (s, 6H), 1.88 (s, 6H), 3.68 (s,1H), 7.41-7.53 (m, 4H), 7.98-8.07 (m, 2H), 8.34-8.43 (m, 2H), 8.49 (s,1H)

Mass Spectrum (EI-MS, m/z): 356 (M⁺)

Synthesis of Complex 22

Under a nitrogen atmosphere, to a toluene solution (31 mL) of1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.43 g,4.00 mmol) and triethylamine (2.02 g, 20.00 mmol), a 1.65 M hexanesolution of n-butyllithium (2.67 mL, 4.40 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 8 hours. The resultantmixture was cooled to −78° C., and a solution of titanium tetrachloride(0.83 g, 4.40 mmol) dissolved in toluene (4 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature overnight. Afterthe completion of the reaction, the solvent was removed under reducedpressure. Thereafter, the residue, to which heptane was added, wasfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. Pentane was added and the resultant solid substancewas filtrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 22 (0.087 g, yield 4.3%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 1.10 (s, 6H), 2.29 (s, 6H), 2.33 (s, 6H),7.30-7.48 (m, 4H), 8.01 (d, J=8.6 Hz, 2H), 8.21 (d, J=9.1 Hz, 2H), 8.51(s, 1H)

Mass Spectrum (EI-MS, m/z): 508 (M⁺)

Example 23 Synthesis of[1-(cyclotetramethylene)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 23”) Synthesis of1-(cyclotetramethylene)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.82 g, 34.09 mmol in terms of pure sodium hydrde) andtetrahydrofuran (39 mL) were mixed. This mixture was heated to 50° C.and aniline (0.21 g, 2.27 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(3.06 g, 25.00 mmol) dissolved in tetrahydrofuran (10 mL) was addeddropwise and stirred at 50° C. for 3 hours, and then was cooled to 0° C.To this solution, a solution of chloro(cyclotetramethylene)phenylsilane(4.47 g, 22.73 mmol) dissolved in toluene (10 mL) was added dropwise andstirred at room temperature for 5 hours. The resultant mixture was addeddropwise at 0° C. to a 10% aqueous sodium carbonate solution (50 ml).Toluene (70 mL) was added to separate an organic phase, and the organicphase was washed with water (70 mL) twice and further washed withsaturated brine (50 mL). The organic phase was dried over sodium sulfateand filtrated. The solvent was removed under reduced pressure andpurification was performed by silica gel column chromatography to obtain1-(cyclotetramethylene)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene(4.35 g, yield 67.8%).

¹H-NMR (CDCl₃, δppm): 0.87-0.98 (m, 4H), 1.55-1.68 (m, 4H), 1.58 (s,6H), 1.91 (s, 6H), 3.11 (s, 1H), 7.16-7.33 (m, 5H)

Mass Spectrum (EI-MS, m/z): 282 (M⁺)

Synthesis of Complex 23

Under a nitrogen atmosphere, to a toluene solution (31 mL) of1-(cyclotetramethylene)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene(1.41 g, 5.00 mmol) and triethylamine (2.53 g, 25.00 mmol), a 1.67 Mhexane solution of n-butyllithium (3.29 mL, 5.50 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature for 6 hours. Theresultant mixture was cooled to −78° C. and a solution of titaniumtetrachloride (1.04 g, 5.50 mmol) dissolved in toluene (6 mL) was addeddropwise at the same temperature. After the mixture was gradually warmedto room temperature, stirring was performed at room temperatureovernight. After the completion of the reaction, the solvent was removedunder reduced pressure. Thereafter, the residue, to which heptane wasadded, was filtrated to remove insoluble materials. The solvent wasremoved to concentrate the filtrate under reduced pressure. Furthermore,to the resultant residue, diethyl ether was added and filtrated toremove insoluble materials. The solvent was removed to concentrate thefiltrate under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 23 (0.13 g, yield 6.1%)as an orange solid.

¹H-NMR (CDCl₃, δppm): 1.18-1.35 (m, 2H), 1.49-1.68 (m, 2H), 1.69-1.99(m, 4H), 2.36 (s, 6H), 2.50 (s, 6H), 7.28-7.40 (m, 5H)

¹³C-NMR (CDCl₃, δppm): 13.25, 14.26, 17.36, 26.85, 128.14, 129.49,133.93, 137.08, 138.26, 142.19, 144.70

Mass Spectrum (EI-MS, m/z): 434 (M⁺)

Example 24 Synthesis of[1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 24”) Synthesis of1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride (0.98 g, 40.95 mmol in termsof pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (57mL) were mixed. This mixture was heated to 50° C. and aniline (0.25 g,2.73 mmol) was added and stirred at 50° C. for one hour. To this, asolution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.67 g, 30.03 mmol)dissolved in tetrahydrofuran (14 mL) was added dropwise and stirred at50° C. for 2 hours, and then was cooled to 0° C. To this solution, asolution of chloromethyldi(4-methylphenyl)silane (7.12 g, 27.30 mmol)dissolved in toluene (14 mL) was added dropwise and stirred at 35° C.The resultant mixture was added dropwise at 0° C. to a mixed solution ofa 10% sodium hydrogen carbonate (36 mL) and a 10% sodium carbonate (36mL). Toluene (36 mL) was added to separate an organic phase, and theorganic phase was dried over sodium sulfate and filtrated. The solventwas removed under reduced pressure and purification was performed bysilica gel column chromatography to obtain1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (3.74g, yield 39.5%).

¹H-NMR (CDCl₃, δppm): 0.30 (s, 3H), 1.55 (s, 6H), 1.73 (s, 6H), 2.33 (s,6H), 3.40 (s, 1H), 7.13 (d, J=8.0 Hz, 4H), 7.39 (d, J=8.0 Hz, 4H)

¹³C-NMR (CDCl₃, δppm): −6.69, 11.10, 14.49, 21.47, 53.03, 128.37,128.62, 133.23, 134.56, 135.27, 138.77

Mass Spectrum (EI-MS, m/z): 346 (M⁺)

Synthesis of Complex 24

Under a nitrogen atmosphere, to a toluene solution (60 mL) of1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (3.00g, 8.66 mmol) and triethylamine (4.38 g, 43.32 mmol), a 1.67 M hexanesolution of n-butyllithium (6.23 mL, 10.40 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at room temperature for 5 hours. The resultantmixture was cooled to −78° C. and a solution of titanium tetrachloride(1.81 g, 9.53 mmol) dissolved in toluene (10 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature and the mixture was stirred at room temperature overnight.After the completion of the reaction, the solvent was removed underreduced pressure. Thereafter, the residue, to which heptane was added,was filtrated to remove insoluble materials. The solvent was removedunder reduced pressure. Pentane was added and the resultant solid wasfiltrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 24 (1.24 g, yield 28.6%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 1.06 (s, 3H), 2.13 (s, 6H), 2.33 (s, 6H), 2.36 (s,6H), 7.17 (d, J=7.9 Hz, 4H), 7.34 (d, J=7.9 Hz, 4H)

¹³C-NMR (CDCl₃, δppm): −0.86, 14.26, 17.72, 21.55, 128.92, 131.62,135.39, 138.30, 139.84, 142.31, 145.33

Mass Spectrum (EI-MS, m/z): 498 (M⁻)

Example 25 Synthesis of[1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (Hereinafter, Referred to as “Complex 25”) Synthesis of1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene

Under a nitrogen atmosphere, sodium hydride dispersed in mineral oil waswashed with hexane to remove the mineral oil. Thereafter, the resultantsodium hydride (0.66 g, 27.27 mmol in terms of pure sodium hydride) andtetrahydrofuran (31 mL) were mixed. This mixture was heated to 50° C.and aniline (0.17 g, 1.82 mmol) was added and stirred at 50° C. for onehour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene(2.44 g, 20.00 mmol) dissolved in tetrahydrofuran (8 mL) was addeddropwise and stirred at 50° C. for 2.5 hours, and then was cooled to 0°C. To this solution, a solution ofchloromethylbis(3,5-dimethylphenyl)silane (5.25 g, 18.18 mmol) dissolvedin toluene (8 mL) was added dropwise and stirred at room temperature for5 hours. The resultant mixture was added dropwise at 0° C. to a 10%aqueous sodium carbonate solution (50 ml). Toluene (50 mL) was added toseparate an organic phase, and the organic phase was washed with water(50 mL) twice and further washed with saturated brine (50 mL). Theorganic phase was dried over sodium sulfate and filtrated. The solventwas removed under reduced pressure and purification was performed bysilica gel column chromatography to obtain1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(5.08 g, yield 74.6%).

¹H-NMR (CDCl₃, δppm): 0.30 (s, 3H), 1.54 (s, 6H), 1.74 (s, 6H), 2.29 (s,12H), 3.40 (s, 1H), 6.97 (s, 2H), 7.10 (s, 4H)

Mass Spectrum (EI-MS, m/z): 374 (M⁺)

Synthesis of Complex 25

Under a nitrogen atmosphere, to a toluene solution (39 mL) of1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene(1.87 g, 5.00 mmol) and triethylamine (2.53 g, 25.00 mmol), a 1.65 Mhexane solution of n-butyllithium (3.64 mL, 6.00 mmol) was addeddropwise at −78° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at 40° C. for 6 hours. The resultantmixture was cooled to −78° C., and a solution of titanium tetrachloride(1.04 g, 5.50 mmol) dissolved in toluene (6 mL) was added dropwise atthe same temperature. After the mixture was gradually warmed to roomtemperature, stirring was performed at room temperature overnight. Afterthe completion of the reaction, the solvent was removed under reducedpressure. Thereafter, the residue, to which heptane was added, wasfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. Pentane was added and the resultant solid wasfiltrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 25 (0.34 g, yield 12.9%) as anorange solid.

¹H-NMR (CDCl₃, δppm): 1.06 (s, 3H), 2.13 (s, 6H), 2.28 (s, 12H), 2.34(s, 6H), 7.06 (s, 6H)

¹³C-NMR (CDCl₃, δppm): −0.76, 14.32, 17.76, 21.39, 131.61, 133.04,134.85, 137.29, 138.77, 142.28, 145.27

Mass Spectrum (EI-MS, m/z): 526 (M⁻)

Example 26 Synthesis of[3-tert-butyl-1-dimethylphenylsilylcyclopentadienyl]titanium trichloride(Hereinafter, Referred to as “Complex 26”) Synthesis of1-dimethylphenylsilyl-tert-butylcyclopentadiene

Under a nitrogen atmosphere, to a tetrahydrofuran solution (30 mL) oftert-butylcyclopentadienyllithium (1.50 g, 11.71 mmol), a solution ofdimethylphenylsilyl chloride (2.20 g, 12.88 mmol) dissolved in toluene(11 mL) was added dropwise at −30° C. After the mixture was warmed toroom temperature, stirring was performed overnight. The resultantmixture was added dropwise at 0° C. to a mixed solution of a 10% sodiumhydrogen carbonate (11 mL) and a 10% sodium carbonate (11 mL). Toluene(11 mL) was added to separate an organic phase, and the organic phasewas dried over sodium sulfate and filtrated. The solvent was removedunder reduced pressure to obtain1-dimethylphenylsilyl-tert-butylcyclopentadiene (2.84 g, yield 94.8%) asa mixture of regioisomers.

¹H-NMR (CDCl₃, δppm) (major isomer): 0.17 (s, 6H), 1.14 (s, 9H), 3.45(s, 1H), 6.05 (s, 1H), 6.45 (d, J=4.8 Hz, 1H), 6.61 (d, J=4.8 Hz, 1H),7.31-7.41 (m, 3H), 7.48-7.56 (m, 2H)

Mass Spectrum (EI-MS, m/z): 256 (M⁺)

Synthesis of 1-dimethylphenylsilyl-tert-butylcyclopentadienyllithium

Under a nitrogen atmosphere, to a hexane solution (38 mL) of1-dimethylphenylsilyl-tert-butylcyclopentadiene (1.92 g, 7.50 mmol), a1.67 M hexane solution of n-butyllithium (5.39 mL, 9.00 mmol) was addeddropwise at 0° C. After the mixture was gradually warmed to roomtemperature, stirring was performed at 40° C. Diethyl ether was added toobtain a white solid, which was filtrated and washed with a small amountof pentane, and then, dried under reduced pressure to obtain1-dimethylphenylsilyl-tert-butylcyclopentadienyllithium (0.28 g, yield14.3%) as a white solid.

Synthesis of 3-tert-butyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene

Under a nitrogen atmosphere, to a tetrahydrofuran solution (34 mL) of1-dimethylphenylsilyl-tert-butylcyclopentadienyllithium (1.68 g, 6.40mmol), a solution of dimethylphenylsilyl chloride (1.20 g, 7.04 mmol)dissolved in toluene (6 mL) was added dropwise at −30° C. After themixture was warmed to room temperature, stirring was performedovernight. The resultant mixture was added dropwise at 0° C. to a mixedsolution of a 10% sodium hydrogen carbonate (17 mL) and a 10% sodiumcarbonate (17 mL). Toluene (17 mL) was added to separate an organicphase, and the organic phase was dried over sodium sulfate andfiltrated. The solvent was removed under reduced pressure andpurification was performed by silica gel column chromatography to obtain3-tert-butyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene (0.64 g, yield25.7%).

¹H-NMR (CDCl₃, δppm): −0.07 (s, 6H), −0.07 (s, 6H), 1.01 (s, 9H), 6.16(dd, J=2.5, 1.6 Hz, 1H), 6.51 (dd, J=4.6, 2.5 Hz, 1H), 6.56 (dd, J=4.6,1.6 Hz, 1H), 7.17-7.27 (m, 6H), 7.27-7.36 (m, 4H)

Mass Spectrum (EI-MS, m/z): 348 (M⁺)

Synthesis of Complex 26

Under a nitrogen atmosphere, to a toluene solution (15 mL) of3-tert-butyl-1,1-bis(dimethylphenylsilyl)cyclopentadiene (0.64 g, 1.65mmol), a solution of titanium tetrachloride (0.31 g, 1.65 mmol)dissolved in toluene (4 mL) was added dropwise at −30° C. The mixedsolution was heated to room temperature and stirring was performed for 3weeks. After the completion of the reaction, the solvent was removedunder reduced pressure to obtain complex 26 (0.30 g, yield 44.5%) as anorange solid substance.

¹H-NMR (CDCl₃, δppm): 0.65 (s, 3H), 0.70 (s, 3H), 1.37 (s, 9H), 7.05(dd, J=3.1, 2.0 Hz, 1H), 7.07 (dd, J=3.1, 2.3 Hz, 1H), 7.21 (dd, J=2.3,2.1 Hz, 1H), 7.33-7.44 (m, 3H), 7.46-7.53 (m, 2H)

¹³C-NMR (CDCl₃, δppm): −2.40, −1.80, 30.89, 34.56, 123.69, 127.01,128.11, 129.18, 129.80, 133.97, 136.27, 142.45, 160.05

Mass Spectrum (EI-MS, m/z): 408 (M⁻)

Example 27 Synthesis of[1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]zirconiumtrichloride (Hereinafter, Referred to as “Complex 27”)

Under a nitrogen atmosphere, to a toluene solution (22 mL) of1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.11 g,3.73 mmol) and triethylamine (1.89 g, 18.64 mmol), a 1.67 M hexanesolution of n-butyllithium (2.68 mL, 4.47 mmol) was added dropwise at−78° C. After the mixture was gradually warmed to room temperature,stirring was performed at 35° C. for 3 hours. The resultant mixture wasadded dropwise to a suspension of zirconium tetrachloride (0.96 g, 4.10mmol) in toluene (4 mL) at −78° C. The resultant mixture was heated toroom temperature and stirred overnight. After the completion of thereaction, the solvent was removed under reduced pressure. Thereafter,the residue, to which heptane was added, was filtrated to removeinsoluble materials. The solvent was removed under reduced pressure.Pentane was added and cooled to −20° C. The resultant solid wasfiltrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 27 (0.56 g, yield 27.4%) as apale yellow solid. The resultant complex contained 0.5 molecules oftriethylamine per molecule.

¹H-NMR (CDCl₃, δppm): 0.71 (s, 3H), 0.86 (t, J=7.1 Hz, 3H), 1.02 (t,J=7.2 Hz, NEt₃), 1.14-1.42 (m, 6H), 2.07 (s, 3H), 2.09 (s, 3H), 2.13 (s,3H), 2.30 (s, 3H), 2.64 (q, J=7.2 Hz, NEt₃), 7.26-7.34 (m, 3H),7.37-7.44 (m, 2H)

¹³C-NMR (CD₂Cl₂, δppm): −2.39, 10.38, 13.26, 13.36, 13.95, 15.94, 16.67,16.88, 26.58, 27.05, 45.67, 128.05, 129.24, 134.73, 137.94; Cp ringcarbons observed as broad signals around 135.15, 135.67 and 139.01.

Mass Spectrum (EI-MS, m/z): 435 (M⁺-Bu)

Example 28 Synthesis of[1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]hafniumtrichloride (Hereinafter, Referred to as “Complex 28”)

Under a nitrogen atmosphere, to a toluene solution (27 mL) of1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene (1.36 g, 5.30mmol) and triethylamine (2.68 g, 26.50 mmol), a 1.67 M hexane solutionof n-butyllithium (3.81 mL, 6.36 mmol) was added dropwise at −78° C.After the mixture was gradually warmed to room temperature, stirring wasperformed at 35° C. for 5.5 hours. The resultant mixture was addeddropwise to a suspension of hafnium tetrachloride (1.87 g, 5.83 mmol) intoluene (10 mL) at −78° C. The mixture was warmed and stirring wasperformed at room temperature overnight. After the completion of thereaction, the solvent was removed under reduced pressure. Thereafter,the residue, to which heptane was added, was filtrated to removeinsoluble materials. The solvent was removed to concentrate the filtrateunder reduced pressure. Pentane was added and the resultant solid wasfiltrated and washed with a small amount of pentane, and then, driedunder reduced pressure to obtain complex 28 (0.48 g, yield 16.8%) as apale yellow solid. The solvent was further removed under reducedpressure. The resultant solid was filtrated and washed with a smallamount of pentane, and then, dried under reduced pressure to obtaincomplex 28 (0.38 g, yield 13.3%) as a pale yellow solid. To theinsoluble materials removed by adding heptane, toluene was added andfiltrated to further remove toluene-insoluble materials. The solvent wasremoved under reduced pressure. Pentane was added and the resultantsolid was filtrated and washed with a small amount of pentane, and then,dried under reduced pressure to obtain complex 28 (0.42 g, yield 14.8%)as a pale yellow solid.

¹H-NMR (CD₂Cl₂, δppm): 0.68 (s, 6H), 2.27 (s, 6H), 2.33 (s, 6H),7.29-7.39 (m, 3H), 7.42-7.48 (m, 2H)

¹³C-NMR (CD₂Cl₂, δppm): 0.47, 12.41, 15.72, 124.69, 128.34, 129.76,133.69, 134.34, 135.58, 138.40

Mass Spectrum (EI-MS, m/z): 540 (M⁺)

Example 29 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]trimethyltitanium(Hereinafter, Referred to as “Complex 29”)

Under a nitrogen atmosphere, to a diethyl ether solution (15 mL) of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.30 g, 0.57 mmol), a 0.93 M diethyl ether solution ofmethylmagnesium iodide (1.91 mL, 1.78 mmol) was added dropwise at −78°C. The mixture was gradually warmed to 0° C. while stirring. After thecompletion of the reaction, the solvent was removed under reducedpressure. Thereafter, to the residue, hexane was added and filtrated toremove insoluble materials. The solvent was removed under reducedpressure. The resultant solid was dried under reduced pressure to obtaincomplex 29 (0.23 g, yield 86.3%) as a pale yellow solid.

¹H-NMR (CD₂Cl₂, δppm): 0.95 (s, 9H), 1.62 (s, 6H), 1.95 (s, 6H),7.27-7.43 (m, 9H), 7.50-7.60 (m, 6H)

¹³C-NMR (CD₂Cl₂, δppm): 12.47, 15.47, 63.59, 116.34, 128.00, 129.76,130.58, 135.78, 136.33, 137.13

Mass Spectrum (EI-MS, m/z): 472 (M⁺)

Example 30 Synthesis of[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]trimethyltitanium(Hereinafter, Referred to as “Complex 30”)

Under a nitrogen atmosphere, to a diethyl ether solution (5 mL) of[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (87.0 mg, 0.14 mmol), a 3.00 M tetrahydrofuran solution ofmethylmagnesium chloride (0.23 mL, 0.70 mmol) was added dropwise at −20°C. The mixture was gradually warmed to room temperature while stirring.After the completion of the reaction, the solvent was removed underreduced pressure. Thereafter, to the residue, hexane was added andfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. The resultant solid was dried under reduced pressureto obtain complex 30 (57.3 mg, yield 73.1%) as a pale yellow solid.

¹H-NMR (CD₂Cl₂, 6 ppm): 0.95 (s, 9H), 1.60 (s, 6H), 1.95 (s, 6H), 2.26(s, 18H), 7.02 (s, 3H), 7.11 (s, 6H)

¹³C-NMR (CD₂Cl₂, 6 ppm): 12.47, 15.53, 21.47, 63.32, 117.74, 129.08,130.62, 131.25, 134.77, 135.68, 137.15

Example 31 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtriphenoxide (Hereinafter, Referred to as “Complex 31”)

Under a nitrogen atmosphere, to a toluene solution (10 mL) of lithiumphenoxide (0.34 g, 3.37 mmol), a toluene solution (10 mL) of(1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl)titaniumtrichloride (0.50 g, 0.94 mmol) was added dropwise at −30° C. Themixture was gradually warmed to room temperature while stirring. Afterthe completion of the reaction at room temperature for 20 hours,additional lithium phenoxide (0.10 g, 1.00 mmol) was added and a smallamount of tetrahydrofuran was added. After the solvent was removed underreduced pressure, hexane was added to the residue and filtrated toremove insoluble materials. The solvent was removed under reducedpressure and recrystallization was performed from toluene/pentane at−20° C. to obtain complex 31 (0.47 g, yield 71.2%) as a yellow solid.

¹H-NMR (CDCl₃, δppm): 1.87 (s, 6H), 2.14 (s, 6H), 6.59 (d, J=7.4 Hz,6H), 6.80 (t, J=7.4 Hz, 3H), 7.08 (t, J=7.4 Hz, 6H), 7.26 (t, J=7.4 Hz,6H), 7.37 (t, J=7.4 Hz, 3H), 7.61 (d, J=7.4 Hz, 6H)

¹³C-NMR (CDCl₃, δppm): 12.06, 15.23, 118.88, 120.09, 120.68, 127.77,128.97, 129.39, 131.92, 134.83, 136.71, 137.38, 164.90

Mass Spectrum (EI-MS, m/z): 706 (M⁺)

Example 32 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtriethoxide (Hereinafter, Referred to as “Complex 32”)

Under a nitrogen atmosphere, to a tetrahydrofuran solution (5 mL) ofmagnesium diethoxide (74.7 mg, 0.65 mmol), a tetrahydrofuran solution (5mL) of (1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl)titaniumtrichloride (193.6 mg, 0.36 mmol) was added dropwise at −30° C. andgradually heated to room temperature while stirring. After thecompletion of the reaction at room temperature for 18 hours, additionalmagnesium diethoxide (32.0 mg, 0.28 mmol) was added. After the solventwas removed under reduced pressure, heptane was added to the residue andfiltrated to remove insoluble materials. The solvent was removed underreduced pressure. Pentane was added and filtrated at −20° C. to removeinsoluble materials. The solvent was removed under reduced pressure toobtain complex 32 (152.6 mg, yield 74.8%) as yellow oil. The resultantcomplex 32 was crystallized by standing at −20° C.

¹H-NMR (CD₂Cl₂, δppm): 1.12 (t, J=6.9 Hz, 9H), 1.66 (s, 6H), 1.99 (s,6H), 4.22 (q, J=6.9 Hz, 6H), 7.28-7.41 (m, 9H), 7.64-7.70 (m, 6H)

¹³C-NMR (CDCl₃, δppm): 11.43, 14.60, 20.02, 70.04, 112.53, 127.13,127.81, 129.38, 132.06, 136.51, 137.07

Mass Spectrum (EI-MS, m/z): 562 (M⁺)

Example 33 Synthesis of Complex 29

A reaction is performed in the same manner as in Example 29 except thata 1.12 M diethyl ether solution (1.83 mL, 2.05 mmol) of methyllithium isused instead of the 0.93 M diethyl ether solution (1.91 mL, 1.78 mmol)of methylmagnesium iodide to obtain complex 29.

Example 34 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]methyltitaniumdichloride

Under a nitrogen atmosphere, to a diethyl ether solution (15 mL) of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.30 g, 0.57 mmol), a 0.93 M diethyl ether solution ofmethylmagnesium iodide (0.63 mL, 0.59 mmol) is added dropwise at −78° C.The temperature is gradually increased to 0° C. while stirring to obtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]methyltitaniumdichloride.

Example 35 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]dimethyltitaniumchloride

Under a nitrogen atmosphere, to a diethyl ether solution (15 mL) of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.30 g, 0.57 mmol), a 0.93 M diethyl ether solution ofmethylmagnesium iodide (1.26 mL, 1.18 mmol) is added dropwise at −78° C.The temperature is gradually increased to 0° C. while stirring to obtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]dimethyltitaniumchloride.

Example 36 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]tribenzyltitanium

Under a nitrogen atmosphere, to a tetrahydrofuran solution (15 mL) of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.30 g, 0.57 mmol), a 0.96 M tetrahydrofuran solution ofbenzylmagnesium chloride (1.85 mL, 1.80 mmol) is added dropwise at −78°C. The temperature is gradually increased to 0° C. while stirring toobtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]tribenzyltitanium.

Example 37 Synthesis of Complex 31

A reaction is performed in the same manner as in Example 30 except that3.00 M tetrahydrofuran solution (0.94 mL, 2.82 mmol) of methylmagnesiumchloride and phenoxy magnesium chloride (0.43 g, 2.82 mmol) generatedfrom phenol (0.27 g, 2.82 mmol) are used instead of the toluene solutionof lithium phenoxide (0.34 g, 3.37 mmol) to obtain complex 31.

Example 38 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]dichlorotitaniumphenoxide

Under a nitrogen atmosphere, to a tetrahydrofuran solution (10 mL) oflithium phenoxide (0.11 g, 1.12 mmol), a tetrahydrofuran solution (10mL) of [1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.50 g, 0.94 mmol) is added dropwise at −30° C. Thetemperature is gradually increased to 0° C. while stirring to obtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]dichlorotitaniumphenoxide.

Example 39 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]chlorotitaniumdiphenoxide

Under a nitrogen atmosphere, to a tetrahydrofuran solution (10 mL) oflithium phenoxide (0.22 g, 2.24 mmol), a tetrahydrofuran solution (10mL) of [1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (0.50 g, 0.94 mmol) is added dropwise at −30° C. Thetemperature is gradually increased to 0° C. while stirring to obtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]chlorotitaniumdiphenoxide.

Example 40 Synthesis of[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrimethoxide

A reaction is performed in the same manner as in Example 31 except thata 1.57 M hexane solution (0.36 mL, 1.08 mmol) of n-butyllithium andlithium methoxide (4.1 mg, 1.08 mmol) generated from methanol (3.5 mg,1.08 mmol) are used instead of the tetrahydrofuran solution of magnesiumdiethoxide (74.7 mg, 0.65 mmol) to obtain[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrimethoxide.

<Production of 1-Hexene>

(1) Activity of 1-Hexene

Analysis was made using gas chromatography (Shimadzu GC-2010, DB-1column).

(2) Synthesis of Publicly-Known Transition Metal Complex

[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride(hereinafter, referred to as “complex 33”) was synthesized in accordancewith a well known method (J. Organomet. Chem. 1999, 592, pp 84-94.).[1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titaniumtrichloride (hereinafter, referred to as “complex 34”) was synthesizedin accordance with a well known method (Organometallics 2002, 21, pp5122-5135.).

Example 41

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied and the interior temperature of the system was increased to40° C., a hexane solution (0.41 mL) of methylaluminoxane having amethylaluminoxane (PMAO-s manufactured by Tosoh Finechem Corp.)concentration of 2.45 mmol/mL was supplied. Then, ethylene wasintroduced so as to obtain the partial pressure of 0.5 MPa to stabilizethe system. To the system, 1.0 ml of a toluene solution (1 μmol/ml) ofcomplex 1 was supplied. A reaction was performed at 40° C. for 30minutes while continuously supplying ethylene gas so as to maintain thewhole pressure at a constant value. Thereafter, ethylene was purged andthe content of the autoclave was deashed with ethanol-hydrochloric acidand then filtrated. 1-hexene was obtained at an activity of 4.01×10⁶g/mol-complex h and a polymer was obtained at an activity of 0.52×10⁶g/mol-complex h.

The results are shown in Table 1.

Example 42

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied and the interior temperature of the system was increased to80° C., a hexane solution (0.41 mL) of methylaluminoxane having anmethylaluminoxane (PMAO-s manufactured by Tosoh Finechem Corp.)concentration of 2.45 mmol/mL was supplied. Then, ethylene wasintroduced so as to obtain the partial pressure of 0.5 MPa to stabilizethe system. To the system, 1.0 ml of a toluene solution (1 μmol/ml) ofcomplex 1 was supplied. A reaction was performed at 80° C. for 30minutes while continuously supplying ethylene gas so as to maintain thewhole pressure at a constant value during the reaction. Thereafter,ethylene was purged and the content of the autoclave was deashed withethanol-hydrochloric acid and then filtrated. 1-hexene was obtained atan activity of 1.65×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.14×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 43

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied and the interior temperature of the system was increased to80° C., 0.73 g of a toluene solution (TMAO-s manufactured by TosohFinechem Corp.) of methylaluminoxane having an Al concentration of 9.2wt % (3.4 mmol/g) was supplied. Then, ethylene was introduced so as toobtain the partial pressure of 0.5 MPa to stabilize the system. To thesystem, 1.0 ml of a toluene solution (1 μmol/ml) of complex 1 wassupplied. A reaction was performed at 80° C. for 30 minutes whilecontinuously supplying ethylene gas so as to maintain the whole pressureat a constant value during the reaction. Thereafter, ethylene was purgedand the content of the autoclave was deashed with ethanol-hydrochloricacid and then filtrated. 1-hexene was obtained at an activity of1.96×10⁶ g/mol-complex h and a polymer was obtained at an activity of0.06×10⁶ g/mol-complex h.

Example 44

The same operation was performed as in Example 43 except that complex 2was used instead of complex C0484. As a result, 1-hexene was obtained atan activity of 2.10×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.1×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 45

The same operation was performed as in Example 43 except that complex 9was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.28×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.02×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 46

The same operation was performed as in Example 43 except that complex 5was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.09×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.02×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 47

The same operation was performed as in Example 43 except that complex 3was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.21×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.06×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 48

The same operation was performed as in Example 43 except that complex 6was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.09×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.12×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 49

The same operation was performed as in Example 43 except that complex 7was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.43×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.07×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 50

The same operation was performed as in Example 43 except that complex 4was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.15×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.03×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 51

The same operation was performed as in Example 43 except that complex 11was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 3.71×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.01×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 52

The same operation was performed as in Example 43 except that complex 21was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 0.91×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.04×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 53

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied, the interior temperature of the system was increased to80° C. Then, a toluene solution (0.4 mL) of triisobutylaluminum (TIBA)having a concentration of 1.0 mmol/mL was supplied to the autoclave.Then, ethylene was introduced so as to obtain the partial pressure of0.5 MPa to stabilize the system. To the system, 1.0 ml of a toluenesolution (1 μmol/ml) of complex 9 was supplied. Subsequently, 3 mL of atoluene solution (1 μmol/ml) oftriphenylmethyltetrakis(pentafluorophenyl)borate (TB) was supplied. Areaction was performed at 80° C. for 30 minutes while continuouslysupplying ethylene gas so as to maintain the whole pressure at aconstant value during the reaction. Thereafter, ethylene was purged andthe content of the autoclave was deashed with ethanol-hydrochloric acidand then filtrated. 1-hexene was obtained at an activity of 1.20×10⁶g/mol-complex h and a polymer was obtained at an activity of 0.62×10⁶g/mol-complex h.

The results are shown in Table 1.

Example 54

The same operation was performed as in Example 53 except thatN,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (AB) was usedinstead of triphenylmethyltetrakis(pentafluorophenyl)borate (TB). As aresult, 1-hexene was obtained at an activity of 1.65×10⁶ g/mol-complex hand a polymer was obtained at an activity of 0.32×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 55

The same operation was performed as in Example 53 except that complex 11was used instead of complex 9. As a result, 1-hexene was obtained at anactivity of 3.43×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.10×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 56

The same operation was performed as in Example 54 except that complex 11was used instead of complex 9. As a result, 1-hexene was obtained at anactivity of 4.75×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.12×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 57

The same operation was performed as in Example 43 except that complex 23was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 0.77×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.03×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 58

The same operation was performed as in Example 43 except that complex 24was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 1.61×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.05×10⁶ g/mol-complex h.

The results are shown in Table 1.

Example 59

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied and the interior temperature of the system was increased to80° C., 0.73 g of a toluene solution of methylaluminoxane (TMAO-smanufactured by Tosoh Finechem Corp.) having an Al concentration of 9.2wt % (3.4 mmol/g) was supplied. Then, ethylene was introduced so as toobtain the partial pressure of 2.0 MPa to stabilize the system. To thesystem, 1.0 ml of a toluene solution (1 μmol/ml) of complex 11 wassupplied. A reaction was performed at 80° C. for 30 minutes whilecontinuously supplying ethylene gas so as to maintain the whole pressureat a constant value during the reaction. Thereafter, ethylene was purgedand the content of the autoclave was deashed with ethanol-hydrochloricacid and then filtrated. 1-hexene was obtained at an activity of11.46×10⁶ g/mol-complex h and a polymer was obtained at an activity of0.40×10⁶ g/mol-complex h.

Comparative Example 1

The same operation was performed as in Example 43 except that complex 34was used instead of complex 1. As a result, 1-hexene was obtained at anactivity of 0.58×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.09×10⁶ g/mol-complex h.

The results are shown in Table 1.

Comparative Example 2

An autoclave (0.4 liter) equipped with a stirrer was dried under reducedpressure, purged with argon and then evacuated. After toluene (90 ml)was supplied and the interior temperature of the system was increased to80° C., a 1.22 mL of a hexane solution of methylaluminoxane having amethylaluminoxane (PMAO-s manufactured by Tosoh Finechem Corp.)concentration of 2.45 mmol/mL was supplied. Then, ethylene wasintroduced so as to obtain the partial pressure of 0.5 MPa to stabilizethe system. To the system, 1.0 ml of a toluene solution (1 μmol/ml) ofcomplex 33 was supplied. A reaction was performed at 80° C. for 30minutes while continuously supplying ethylene gas so as to maintain thewhole pressure at a constant value during the reaction. Thereafter,ethylene was purged and the content of the autoclave was deashed withethanol-hydrochloric acid and then filtrated. 1-hexene was obtained atan activity of 0.06×10⁶ g/mol-complex h and a polymer was obtained at anactivity of 0.01×10⁶ g/mol-complex h.

The results are shown in Table 1.

TABLE 1 Aluminum Borate compound compound C′6 activity PE activityAmount Amount Temperature (t/mol (t/mol Complex Type (m mol) Type (μmol) (° C.) complex h*) complex h*) Example 41 1 PMAO 1.0 — — 40 4.010.52 Example 42 1 PMAO 1.0 — — 80 1.65 0.14 Example 43 1 TMAO 2.5 — — 801.96 0.06 Example 44 2 TMAO 2.5 — — 80 2.10 0.10 Example 45 9 TMAO 2.5 —— 80 1.28 0.02 Example 46 5 TMAO 2.5 — — 80 1.09 0.02 Example 47 3 TMAO2.5 — — 80 1.21 0.06 Example 48 6 TMAO 2.5 — — 80 1.09 0.12 Example 49 7TMAO 2.5 — — 80 1.43 0.07 Example 50 4 TMAO 2.5 — — 80 1.15 0.03 Example51 11 TMAO 2.5 — — 80 3.71 0.01 Example 52 21 TMAO 2.5 — — 80 0.91 0.04Example 53 9 TIBA 0.4 TB 3 80 1.20 0.62 Example 54 9 TIBA 0.4 AB 3 801.65 0.32 Example 55 11 TIBA 0.4 TB 3 80 3.43 0.10 Example 56 11 TIBA0.4 AB 3 80 4.75 0.12 Example 57 23 TMAO 2.5 — — 80 0.77 0.03 Example 5824 TMAO 2.5 — — 80 1.61 0.05 Example 59** 11 TMAO 2.5 — — 80 11.5 0.40Comparative 34 TMAO 2.5 — — 80 0.58 0.09 Example 1 Comparative 33 PMAO 3— — 80 0.06 0.01 Example 2 *t = 10⁶ g **The ethylene pressure was set at2.0 MPa in Example 59 only.

<Production of Ethylenic Polymer>

(1) Molecular Weight and Molecular Weight Distribution (Mw/Mn)

Measurement was performed using Rapid GPC (manufactured by Symyx) in thefollowing conditions.

Liquid feeding apparatus: (LC pump) manufactured by Gilson

-   -   Model 305 (pump head 25.SC)

Column: PLgel Mixed-B 10 μm

-   -   Manufactured by Polymer Laboratories (PL)    -   7.5 mm in diameter×300 mm

Mobile phase: o-Dichlorobenzene

Dissolving solvent: 1,2,4-trichlorobenzene

Flow rate: 2 ml/minute

Column temperature: 160° C.

Calibration curve: PL Standard product,

-   -   polystyrene (PS) 8 samples    -   (Standard PS molecular weight)    -   5,000, 10,050, 28,500, 65,500    -   185,400, 483,000, 1,013,000, 3,390,000

(2) Melting Point (Unit: ° C.)

Using a differential scanning calorimeter (DSC 6200R manufactured bySeiko Instruments Inc.), the melting point of a polymer was measured inthe following conditions. The melting point was obtained from thethermogram of the second temperature increase.

[Conditions] 20° C. (20° C./minute)→200° C. (10 minute hold) (−20°C./minute)→−100° C. (10 minute hold) (20° C./minute)→200° C. (10 minutehold)

(3) Number of Butyl Branches

The number of butyl branches in the resultant polymer was obtained frominfrared absorption spectrum. Note that measurement and calculation wereperformed using characteristic absorption due to hexene in accordancewith the method described in a literature (Characterization ofPolyethylene by Infrared Absorption Spectrum written by Takayama andUsami, et al.). The number of butyl branches was indicated in terms ofthe number of branches per 1000 carbon atoms (Me/100° C.).

(4) Synthesis of Publicly-Known Transition Metal Complex

Dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (hereinafter, referred to as “complex 35”) was synthesized inaccordance with a publicly known method (JP 9-87313 A).

Dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (hereinafter, referred to as “complex 36”) was synthesized inaccordance with a publicly known method (JP 2535249B).

Isopropylidenebis(indenyl)hafnium dichloride (hereinafter, referred toas “complex 37”) was synthesized in accordance with a publicly knownmethod (Organometallics (1997), 16 (4), pp 713).

rac-Dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride (hereinafter, referred to as “complex 38”) was synthesized inaccordance with a publicly known method (WO2009/019919).

Diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride(hereinafter, referred to as “complex 39”) was synthesized in accordancewith a publicly known method (JP 3154999B).

1,2-Ethylenebis(indenyl)zirconium diphenoxide (hereinafter, referred toas “complex 40”) was synthesized in accordance with a publicly knownmethod (JP 2003-12682 A).

2-[N-(2,6-diisopropylphenylamide)-o-isopropylphenylmethyl]-6-(2-η¹-naphthyl)-pyridylhafniumdimethyl (hereinafter, referred to as “complex 41”) was synthesized inaccordance with a publicly known method (JP 2006-525314 A).

1,2-Ethylenebis(indenyl)zirconium dichloride (hereinafter, referred toas “complex 42”) was synthesized in accordance with a publicly wellknown method (Organometallics (1995), 14 (1), 5).

Isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (hereinafter, referred to as “complex 43”) was synthesized inaccordance with a publicly known method (JP 9-87313 A).

Dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (hereinafter, referred to as “complex 44”) was synthesized inaccordance with a publicly known method (JP 9-87313 A).

Isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride (hereinafter, referred to as “complex 45”) was synthesized inaccordance with a publicly known method (WO2001/027124).

Dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (hereinafter, referred to as “complex 46”) was synthesized inaccordance with a publicly known method (Macromolecules 2010, 43, pp2299-2306).

Example 60

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 35) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 7 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 21.9×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was4.0×10⁵, Mw/Mn was 1.8, the melting point was 118.3° C. and the numberof butyl branches was 6.

The results are shown in Table 2.

Example 61

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadinyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 6 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 25.7×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was9.4×10⁵, Mw/Mn was 1.7, the melting point was 121.4° C. and the numberof butyl branches was 4.

The results are shown in Table 2.

Example 62

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C. andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadinyl]titaniumtrichloride (complex 1) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 9 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 19.3×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was1.1×10⁶, Mw/Mn was 1.7, the melting point was 118.8° C. and the numberof butyl branches per 1000 carbon atoms was 11.

The results are shown in Table 2.

Example 63

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.005 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.095 μmol ofisopropylidene(bisindenyl)hafnium dichloride (complex 37) was suppliedto initiate the polymerization. The polymerization was performed at 70°C. for 8 minutes. During the polymerization, ethylene gas was suppliedso as to maintain the whole pressure of the autoclave at a constantvalue. After completion of the polymerization, ethylene within theautoclave was purged and the volatile component therein was removed bydistillation under reduced pressure to obtain a polymer. The activitywas 19.7×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was1.1×10⁶, Mw/Mn was 1.8, the melting point was 122.7° C. and the numberof butyl branches was 3.

The results are shown in Table 2.

Example 64

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.09 μmol ofisopropylidene(bisindenyl)hafnium dichloride (complex 37) was suppliedto initiate the polymerization. The polymerization was performed at 70°C. for 13 minutes. During the polymerization, ethylene gas was suppliedso as to maintain the whole pressure of the autoclave at a constantvalue. After the completion of the polymerization, ethylene within theautoclave was purged and the volatile component therein was removed bydistillation under reduced pressure to obtain a polymer. The activitywas 9.8×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was1.3×10⁶, Mw/Mn was 1.7, the melting point was 118.3° C. and the numberof butyl branches was 8.

The results are shown in Table 2.

Example 65

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.005 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.095 μmol ofrac-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride (complex 38) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 36 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 3.1×10⁶ g/mol-complex h.

As the physical properties of the resultant polymer were measured. Mwwas 6.1×10⁵, Mw/Mn was 2.3, the melting point was 121.9° C. and thenumber of butyl branches was 3.

The results are shown in Table 2.

Example 66

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.09 μmol ofrac-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride (complex 38) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 40 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 2.5×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was7.8×10⁵, Mw/Mn was 2.6, the melting point was 119.6° C. and the numberof butyl branches was 8.

The results are shown in Table 2.

Example 67

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.09 μmol ofdiphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride(complex 39) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 4 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 47.0×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured, Mw was5.9×10⁵, Mw/Mn was 1.8, the melting point was 125.2° C. and the numberof butyl branches was 2.

The results are shown in Table 2.

Example 68

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(triphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 9) and 0.09 μmol of ethylene(bisindenyl)zirconiumdiphenoxide (complex 40) was supplied to initiate the polymerization.The polymerization was performed at 70° C. for 2 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 121.2×10⁶ g/mol-complexh.

As the physical properties of the resultant polymer were measured Mw was2.1×10⁵, Mw/Mn was 1.8, the melting point was 129.7° C. and the numberof butyl branches was 5.

The results are shown in Table 2.

Example 69

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(triphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 9) and 0.09 μmol of2-[N-(2,6-diisopropylphenylamide)-o-methylphenylmethyl]-6-(2-η-1-naphthyl)pyridylhafniumdimethyl (complex 41) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 2 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 95.1×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured Mw was3.0×10⁴, Mw/Mn was 1.4, the melting point was 126.2° C. and the numberof butyl branches per 1000 carbon atoms was 9.

The results are shown in Table 2.

Comparative Example 3

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride(complex 33) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 8 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 21.1×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Themelting point was 132.4° C.

The results are shown in Table 2.

Comparative Example 4

In an autoclave, toluene (3.7 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (400 μL) of methylaluminoxane (TMAO manufactured byTosoh Finechem Corp.) having a concentration of 0.25 mmol/mL wassupplied to the autoclave. Then, to the autoclave, a toluene solution(900 μL) of 0.01 μmol of[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride(complex 33) and 0.09 μmol of ethylene(bisindenyl)zirconium dichloride(complex 42) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 6 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 34.4×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured. Themelting point was 132.8° C.

The results are shown in Table 2.

Example 70

In an autoclave, 1-hexene (0.02 ml) and toluene (3.7 ml) were placedunder a nitrogen atmosphere. The interior temperature was increased to70° C., and ethylene was pressurized to 0.60 MPa to stabilize thesystem. Then, a toluene solution (400 μL) of methylaluminoxane (TMAOmanufactured by Tosoh Finechem Corp.) having a concentration of 0.25mmol/mL was supplied to the autoclave. Then, to the autoclave, a toluenesolution (900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 35) was supplied to initiate the polymerization. Thepolymerization was performed at 70° C. for 8 minutes. During thepolymerization, ethylene gas was supplied so as to maintain the wholepressure of the autoclave at a constant value. After the completion ofthe polymerization, ethylene within the autoclave was purged and thevolatile component therein was removed by distillation under reducedpressure to obtain a polymer. The activity was 15.9×10⁶ g/mol-complex h.

The physical properties of the resultant polymer were measured, Mw was2.7×10⁵, Mw/Mn was 2.3, the melting point was 105.7° C. and the numberof butyl branches was 18.

The results are shown in Table 2.

TABLE 2 Time polym. trim, trim. cat. Me/ act t/ Mw/ min cocat* cat.**cat.*** mol % Tm(° C.) 1000 C molh**** Mw Mn Example 60 7 TMAO(tol) 35 15 118.3 6 21.9 400000 1.8 Example 61 6 TMAO(tol) 36 1 5 121.4 4 25.7940000 1.7 Example 62 9 TMAO(tol) 36 1 10 118.8 11 19.3 1100000 1.7Example 63 8 TMAO(tol) 37 2 5 122.7 3 19.7 1100000 1.8 Example 64 13TMAO(tol) 37 2 10 118.3 8 9.8 1300000 1.7 Example 65 36 TMAO(tol) 38 2 5121.9 3 3.1 610000 2.3 Example 66 40 TMAO(tol) 38 2 10 119.6 8 2.5780000 2.6 Example 67 4 TMAO(tol) 39 2 10 125.2 2 47.0 590000 1.8Example 68 2 TMAO(tol) 40 9 10 129.7 5 121.2 210000 1.8 Example 69 2TMAO(tol) 41 9 10 126.2 9 95.1 30000 1.4 Example 70 8 TMAO(tol) 35 1 5105.7 18 15.9 270000 2.3 Comparative 8 TMAO(tol) 36 33 10 132.4 — 21.1 —— Example 3 Comparative 6 TMAO(tol) 42 33 10 132.8 — 34.4 — — Example 4*co cat = activating co-catalytic component **polym. cat. = catalyticcomponent for polymerization ***trim. cat. = catalytic component fortrimerization ****t = 10⁶ g

Example 71

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 35) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 3minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 63.5×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was3.4×10⁵, Mw/Mn was 1.7, the melting point was 128.1° C. and the numberof butyl branches was 2.

The results are shown in Table 3.

Example 72

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.09 μmol ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 35) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 3minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 45.8×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was3.8×10⁵, Mw/Mn was 1.9, the melting point was 122.1° C. and the numberof butyl branches was 5.

The results are shown in Table 3.

Example 73

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofisopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 43) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 2minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 69.0×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured, Mw was1.2×10⁵, Mw/Mn was 1.5, the melting point was 121.6° C. and the numberof butyl branches was 9.

The results are shown in Table 3.

Example 74

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.09 μmol ofisopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 43) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 2minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 72.4×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was7.9×10⁴, Mw/Mn was 1.5, the melting point was 120.2° C. and the numberof butyl branches was 20.

The results are shown in Table 3.

Example 75

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 44) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 3minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 54.0×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was1.8×10⁵, Mw/Mn was 1.5, the melting point was 118.7° C. and the numberof butyl branches was 7.

The results are shown in Table 3.

Example 76

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.005 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.095 μmol ofdimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (complex 46) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 2minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 82.5×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was2.5×10⁵, Mw/Mn was 1.6, the melting point was 128.4° C. and the numberof butyl branches was 2.

The results are shown in Table 3.

Example 77

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 8minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 17.4×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was7.1×10⁵, Mw/Mn was 2.4, the melting point was 123.9° C. and the numberof butyl branches was 8.

The results are shown in Table 3.

Example 78

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.09 μmol ofrac-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]hafniumdichloride (complex 38) and a toluene solution (300 μL) oftriphenylmethyltetrakis(pentafluorophenyl)borate (TB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 60minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 6.0×10⁵g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was5.6×10⁵, Mw/Mn was 2.5, the melting point was 128.6° C. and the numberof butyl branches was 5.

The results are shown in Table 3.

Example 79

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied the autoclave. Then, to theautoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 2) and 0.09 μmol of isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride (complex 45) and a toluene solution (300 μL) oftriphenylmethyltetrakis(pentafluorophenyl)borate (TB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 3minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 42.1×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was3.5×10⁵, Mw/Mn was 1.8, the melting point was 129.3° C. and the numberof butyl branches was 3.

The results are shown in Table 3.

Comparative Example 5

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride(complex 33) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) and a toluene solution (300 μL) ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (AB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 6minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 23.1×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Themelting point was 134.5° C.

The results are shown in Table 3.

Comparative Example 6

In an autoclave, toluene (3.64 ml) was placed under a nitrogenatmosphere. The interior temperature was increased to 70° C., andethylene was pressurized to 0.60 MPa to stabilize the system. Then, atoluene solution (160 μL) of triisobutylaluminum (TIBA) having aconcentration of 0.25 mmol/mL was supplied to the autoclave. Then, tothe autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride(complex 33) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) and a toluene solution (300 μL) oftriphenylmethyltetrakis(pentafluorophenyl)borate (TB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 2minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 63.0×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Themelting point was 134.8° C.

The results are shown in Table 3.

Example 80

In an autoclave, 1-hexene (0.02 ml) and toluene (3.62 ml) were placedunder a nitrogen atmosphere. The interior temperature was increased to70° C., and ethylene was pressurized to 0.60 MPa to stabilize thesystem. Then, a toluene solution (160 μL) of triisobutylaluminum (TIBA)having a concentration of 0.25 mmol/mL was supplied to the autoclave.Then, to the autoclave, a toluene solution (900 μL) of 0.01 μmol of[1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl]titaniumtrichloride (complex 1) and 0.09 μmol ofdimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride (complex 36) and a toluene solution (300 μL) oftriphenylmethyltetrakis(pentafluorophenyl)borate (TB) having aconcentration of 0.001 mmol/mL were supplied to initiate thepolymerization. The polymerization was performed at 70° C. for 6minutes. During the polymerization, ethylene gas was supplied so as tomaintain the whole pressure of the autoclave at a constant value. Afterthe completion of the polymerization, ethylene within the autoclave waspurged and the a volatile component therein was removed by distillationunder reduced pressure to obtain a polymer. The activity was 19.8×10⁶g/mol-complex h.

The physical properties of the resultant polymer were measured. Mw was3.8×10⁵, Mw/Mn was 2.2, the melting point was 117.8° C. and the numberof butyl branches was 10.

The results are shown in Table 3.

TABLE 3 Time polym. trim. trim. cat Me/ act t/ Mw/ min cocat* cat**cat.*** mol % Tm(° C.) 1000 C molh**** Mw Mn Example 71 3 TIBA/AB 35 1 5128.1 2 63.5 340000 1.7 Example 72 3 TIBA/AB 35 1 10 122.1 5 45.8 3800001.9 Example 73 2 TIBA/AB 43 1 5 121.6 9 69.0 120000 1.5 Example 74 2TIBA/AB 43 1 10 120.2 20 72.4 79000 1.5 Example 75 3 TIBA/AB 44 1 5118.7 7 54.0 180000 1.5 Example 76 2 TIBA/AB 46 1 5 128.4 2 82.5 2500001.6 Example 77 8 TIBA/AB 36 1 10 123.9 8 17.4 710000 2.4 Example 78 60TIBA/TB 38 2 10 128.6 5 0.6 560000 2.5 Example 79 3 TIBA/TB 45 2 10129.3 3 42.1 350000 1.8 Example 80 6 TIBA/TB 36 1 10 117.8 10 19.8380000 2.2 Comparative 6 TIBA/AB 36 33 10 134.5 — 23.1 — — Example 5Comparative 2 TIBA/TB 36 33 10 134.8 — 63.0 — — Example 6 *co cat =activating co-catalytic component **polym. cat. = catalytic componentfor polymerization ***trim. cat. = catalytic component for trimerization****t = 10⁶ g

Example 81

In an autoclave, toluene (3.68 ml) was placed under a nitrogenatmosphere. The interior temperature of the system was increased to 80°C., and ethylene was pressurized to 0.50 MPa to stabilize the system.Then, a toluene solution (160 μL) of triisobutylaluminum having theconcentration of 0.10 mmol/mL was supplied the autoclave. Then, 40 μL oftoluene solution of[1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]trimethyltitanium(complex 30) having the concentration of 0.001 mmol/mL and 120 μL oftoluene solution of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate having the concentration of 0.001mmol/mL were supplied to the autoclave to initiate reaction. Thereaction was performed at 80° C. for 36 minutes. During the reaction,ethylene gas was supplied so as to maintain the total pressure in theautoclave at a constant value. Thereafter, the ethylene was purged andthe supernatant solution of the content of the autoclave was taken andGC-analyzed and the volatile component therein was removed bydistillation under reduced pressure to obtain a polymer. The results areshown in Table 4 and the time-dependent change of the ethyleneabsorption is shown in FIG. 1. The ethylene absorption is presented interms of the cumulative value of the pressure needed for elevating thepressure to the target pressure when the pressure was dropped by theethylene absorption in the reaction in psi unit.

Example 82

The operation was carried out in the same manner as in Example 81 exceptthat the ethylene pressure was changed from 0.50 MPa to 0.80 MPa andthat the reaction time was 12 min. The results are shown in Table 4, andthe time-dependent change of the ethylene absorption is shown in FIG. 2.

Example 83

The operation was carried out in the same manner as in Example 81 exceptthat complex 11 is used instead of complex 30 and that the reaction timewas 60 min. The results are shown in Table 4 and the time-dependentchange of the ethylene absorption is shown in FIG. 3.

TABLE 4 Final 1-hexene temp ethylene conv.* time polymer act.(polymer)GC area % vs complex (° C.) (MPa) (psi) (min) g t/molh** solvent(toluene) Example 81 30 80 0.5 500 36 0.004 0.2 12.2 Example 82 30 800.8 501 12 0.002 0.3 14.3 Example 83 11 80 0.5 289 60 0.001 0.0 8.8Evaluation Condition: TIBA/Complex/AB = 400/1/3 *presented in terms ofthe cumulative value of the pressure needed for elevating the pressureto the target pressure when the pressure was dropped by the ethyleneabsorption in the reaction in psi unit. **t = 10⁶ g

Example 84

In an autoclave, toluene (3.8 ml) was placed under a nitrogenatmosphere. The interior temperature of the system was increased to 80°C., and ethylene was pressurized to 0.50 MPa to stabilize the system.Then, a toluene solution (160 μL) of methylaluminoxane (manufactured byTosoh Finechem Corporation, TMAO) having the concentration of 0.25mmol/mL was supplied to the autoclave. Then, 40 μL of toluene solutionof[1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]trimethyltitanium(complex 29) having the concentration of 0.001 mmol/mL was supplied toinitiate reaction. The reaction was performed at 80° C. for 30 minutes.During the reaction, ethylene gas was supplied so as to maintain thetotal pressure in the autoclave at a constant value. Thereafter, theethylene was purged and the supernatant solution of the content of theautoclave was taken and GC-analyzed, and the volatile component thereinwas removed by distillation under reduced pressure to obtain a polymer.The results are shown in Table 5 and the time-dependent change of theethylene absorption is shown in FIG. 4.

Example 85

The operation was carried out in the same manner as in Example 84 exceptthat complex 9 is used instead of complex 29. The results are shown inTable 5 and the time-dependent change of the ethylene absorption isshown in FIG. 5.

TABLE 5 Final 1-hexene temp ethylene conv.* time polymer act.(polymer)GC area % vs complex (° C.) (MPa) (psi) (min) g t/molh** solvent(toluene) Example 84 29 80 0.5 53 30 0.005 0.3 1.8 Example 85 9 80 0.530 30 0.013 0.7 0.7 Evaluation Condition: TMAO/Complex = 1000/1*presented in terms of the cumulative value of the pressure needed forelevating the pressure to the target pressure when the pressure wasdropped by the ethylene absorption in the reaction in psi unit. **t =10⁶ g

INDUSTRIAL APPLICABILITY

The present invention has high industrial applicability as providing atransition metal complex that serves as a catalytic component capable ofefficiently and highly selectively producing 1-hexene through thetrimerization reaction of ethylene even under high temperatureconditions and also providing a process for economically producing anethylenic polymer having a butyl branch by polymerizing ethylene evenunder high temperature conditions.

1. A transition metal complex represented by general formula (1):

wherein M¹ represents a transition metal atom of Group 4 of the PeriodicTable of the Elements; R¹, R², R³ and R⁴ each independently represent ahydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbonatoms which optionally have a halogen atom as a substituent, an alkoxygroup having 1 to 20 carbon atoms which optionally have a halogen atomas a substituent, an aryl group having 6 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aryloxy group having6 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aralkyl group having 7 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aralkyloxy grouphaving 7 to 20 carbon atoms which optionally have a halogen atom as asubstituent, a substituted silyl group represented by —Si(R¹²)₃, whereinthe three R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, or adisubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, and at least one of R¹, R², R³ and R⁴ is ahalogen atom, the alkyl group, the alkoxy group, the aryl group, thearyloxy group, the aralkyl group, the aralkyloxy group, the substitutedsilyl group or the disubstituted amino group; R⁵ and R⁹ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aryl group having 6 to 20 carbon atoms which optionallyhave a halogen atom as a substituent, an aralkyl group having 7 to 20carbon atoms which optionally have a halogen atom as a substituent, or asubstituted silyl group represented by —Si(R¹²)₃, wherein the three R¹²groups each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20; R⁶, R⁷ and R⁸ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an alkoxy group having 1 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aryl group having 6to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aryloxy group having 6 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aralkyl group having7 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aralkyloxy group having 7 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, a substituted silylgroup represented by —Si(R¹²)₃, wherein the three R¹² groups eachindependently represent a hydrogen atom, a hydrocarbyl group or ahalogenated hydrocarbyl group, and the total number of the carbon atomsin the three R¹² groups is 1 to 20, or a disubstituted amino grouprepresented by —N(R¹³)₂, wherein the two R¹³ groups each independentlyrepresent a hydrocarbyl group or a halogenated hydrocarbyl group, andthe total number of the carbon atoms in the two R¹³ groups is 2 to 20;R¹⁰ is a methyl group, and R¹¹ is an alkyl group having 2 to 20 carbonatoms which optionally have a halogen atom as a substituent or an arylgroup having 6 to 20 carbon atoms which optionally have a halogen atomas a substituent; X¹, X² and X³ each independently represent a hydrogenatom, a halogen atom, an alkyl group having 1 to 20 carbon atoms whichmay have a halogen atom as a substituent, an alkoxy group having 1 to 20carbon atoms which may have a halogen atom as a substituent, an arylgroup having 6 to 20 carbon atoms which may have a halogen atom as asubstituent, an aryloxy group having 6 to 20 carbon atoms which may havea halogen atom as a substituent, an aralkyl group having 7 to 20 carbonatoms which may have a halogen atom as a substituent, an aralkyloxygroup having 7 to 20 carbon atoms which may have a halogen atom as asubstituent, a substituted silyl group represented by —Si(R¹²)₃, whereinthe three R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, or adisubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20; of R¹, R², R³ and R⁴, two groups bonded to twoadjacent carbon atoms are optionally bonded to each other to form a ringtogether with the two carbon atoms to which the two groups are bonded;of R⁵, R⁶, R⁷, R⁸ and R⁹, two groups bonded to two adjacent carbon atomsare optionally bonded to each other to form a ring together with the twocarbon atoms to which the two groups are bonded.
 2. The transition metalcomplex according to claim 1, wherein M¹ in the general formula (1) is atitanium atom.
 3. The transition metal complex according to claim 2,wherein each of R¹, R², R³ and R⁴ in the general formula (1) is ahydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbonatoms which may have a halogen atom as a substituent, an aryl grouphaving 6 to 20 carbon atoms which may have a halogen atom as asubstituent, or an aralkyl group having 7 to 20 carbon atoms which mayhave a halogen atom as a substituent.
 4. The transition metal complexaccording to claim 2, wherein the cyclopentadienyl moiety represented bythe general formula (2) in the general formula (1)

is selected from among methylcyclopentadienyl, ethylcyclopentadienyl,n-propylcyclopentadienyl, isopropylcyclopentadienyl,n-butylcyclopentadienyl, sec-butylcyclopentadienyl,tert-butylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl,tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl,and octahydrofluorenyl.
 5. The transition metal complex according toclaim 2, wherein each of R¹, R², R³ and R⁴ in the general formula (1) isa methyl group.
 6. A transition metal complex represented by generalformula (1):

wherein M¹ represents a transition metal atom of Group 4 of the PeriodicTable of the Elements; R¹, R², R³ and R⁴ each independently represent ahydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbonatoms which optionally have a halogen atom as a substituent, an alkoxygroup having 1 to 20 carbon atoms which optionally have a halogen atomas a substituent, an aryl group having 6 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aryloxy group having6 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aralkyl group having 7 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an aralkyloxy grouphaving 7 to 20 carbon atoms which optionally have a halogen atom as asubstituent, a substituted silyl group represented by —Si(R¹²)₃, whereinthe three R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, or adisubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20, and at least one of R¹, R², R³ and R⁴ is ahalogen atom, the alkyl group, the alkoxy group, the aryl group, thearyloxy group, the aralkyl group, the aralkyloxy group, the substitutedsilyl group or the disubstituted amino group; R⁵ and R⁹ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aryl group having 6 to 20 carbon atoms which optionallyhave a halogen atom as a substituent, an aralkyl group having 7 to 20carbon atoms which optionally have a halogen atom as a substituent, or asubstituted silyl group represented by —Si(R¹²)₃, wherein the three R¹²groups each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20; R⁷ represents a hydrogen atom,a halogen atom, an alkyl group having 1 to 20 carbon atoms whichoptionally have a halogen atom as a substituent, an alkoxy group having1 to 20 carbon atoms which optionally have a halogen atom as asubstituent, an aryl group having 6 to 20 carbon atoms which optionallyhave a halogen atom as a substituent, an aryloxy group having 6 to 20carbon atoms which optionally have a halogen atom as a substituent, anaralkyl group having 7 to 20 carbon atoms which optionally have ahalogen atom as a substituent, an aralkyloxy group having 7 to 20 carbonatoms which optionally have a halogen atom as a substituent, asubstituted silyl group represented by —Si(R¹²)₃, wherein the three R¹²groups each independently represent a hydrogen atom, a hydrocarbyl groupor a halogenated hydrocarbyl group, and the total number of the carbonatoms in the three R¹² groups is 1 to 20, or a disubstituted amino grouprepresented by —N(R¹³)₂, wherein the two R¹³ groups each independentlyrepresent a hydrocarbyl group or a halogenated hydrocarbyl group, andthe total number of the carbon atoms in the two R¹³ groups is 2 to 20,and R⁶ and R⁸ are each an alkyl group having 1 to 20 carbon atoms whichoptionally have a halogen atom as a substituent or an aryl group having6 to 20 carbon atoms which optionally have a halogen atom as asubstituent; R¹⁰ and R¹¹ each independently represent an aryl grouphaving 6 to 20 carbon atoms which optionally have a halogen atom as asubstituent; X¹, X² and X³ each independently represent a hydrogen atom,a halogen atom, an alkyl group having 1 to 20 carbon atoms which mayhave a halogen atom as a substituent, an alkoxy group having 1 to 20carbon atoms which may have a halogen atom as a substituent, an arylgroup having 6 to 20 carbon atoms which may have a halogen atom as asubstituent, an aryloxy group having 6 to 20 carbon atoms which may havea halogen atom as a substituent, an aralkyl group having 7 to 20 carbonatoms which may have a halogen atom as a substituent, an aralkyloxygroup having 7 to 20 carbon atoms which may have a halogen atom as asubstituent, a substituted silyl group represented by —Si(R¹²)₃, whereinthe three R¹² groups each independently represent a hydrogen atom, ahydrocarbyl group or a halogenated hydrocarbyl group, and the totalnumber of the carbon atoms in the three R¹² groups is 1 to 20, or adisubstituted amino group represented by —N(R¹³)₂, wherein the two R¹³groups each independently represent a hydrocarbyl group or a halogenatedhydrocarbyl group, and the total number of the carbon atoms in the twoR¹³ groups is 2 to 20; of R¹, R², R³ and R⁴, two groups bonded to twoadjacent carbon atoms are optionally bonded to each other to form a ringtogether with the two carbon atoms to which the two groups are bonded;of R⁵, R⁶, R⁷, R⁸ and R⁹, two groups bonded to two adjacent carbon atomsare optionally bonded to each other to form a ring together with the twocarbon atoms to which the two groups are bonded.
 7. The transition metalcomplex according to claim 6, wherein M¹ in the general formula (1) is atitanium atom.
 8. The transition metal complex according to claim 7,wherein each of R¹, R², R³ and R⁴ in the general formula (1) is ahydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbonatoms which may have a halogen atom as a substituent, an aryl grouphaving 6 to 20 carbon atoms which may have a halogen atom as asubstituent, or an aralkyl group having 7 to 20 carbon atoms which mayhave a halogen atom as a substituent.
 9. The transition metal complexaccording to claim 7, wherein the cyclopentadienyl moiety represented bythe general formula (2) in the general formula (1)

is selected from among methylcyclopentadienyl, ethylcyclopentadienyl,n-propylcyclopentadienyl, isopropylcyclopentadienyl,n-butylcyclopentadienyl, sec-butylcyclopentadienyl,tert-butylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl,tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl,and octahydrofluorenyl.
 10. The transition metal complex according toclaim 7, wherein each of R¹, R², R³ and R⁴ in the general formula (1) isa methyl group.